WO2014156776A1 - Method for producing dialdehyde - Google Patents

Method for producing dialdehyde Download PDF

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Publication number
WO2014156776A1
WO2014156776A1 PCT/JP2014/057169 JP2014057169W WO2014156776A1 WO 2014156776 A1 WO2014156776 A1 WO 2014156776A1 JP 2014057169 W JP2014057169 W JP 2014057169W WO 2014156776 A1 WO2014156776 A1 WO 2014156776A1
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Prior art keywords
reaction
group
dialdehyde
rhodium
hydrogen
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PCT/JP2014/057169
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French (fr)
Japanese (ja)
Inventor
達也 吉川
辻　智啓
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株式会社クラレ
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Priority to EP14774389.2A priority Critical patent/EP2980060B1/en
Priority to US14/778,784 priority patent/US9464018B2/en
Priority to SG11201507901WA priority patent/SG11201507901WA/en
Priority to CA2907598A priority patent/CA2907598C/en
Priority to CN201480017693.3A priority patent/CN105050996B/en
Priority to JP2015508325A priority patent/JP6255007B2/en
Priority to KR1020157026783A priority patent/KR102204484B1/en
Publication of WO2014156776A1 publication Critical patent/WO2014156776A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/12—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing more than one —CHO group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Definitions

  • the present invention relates to a method for producing dialdehyde. More specifically, the present invention relates to a dihydroxy compound having a linear dialdehyde content of 80 to 90% by mass by hydroformylating a linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular end.
  • the present invention relates to a method for producing an aldehyde industrially advantageously.
  • the method of the present invention is, for example, from 7-octen-1-al to a diol mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol (content of 1,9-nonanediol of 80 to 90).
  • the diol mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol is commercially available from Kuraray Co., Ltd. under the trade name “ND15”, and is a raw material for producing polycarbonate, polyester, polyurethane and the like, paint (polyester paint, Epoxy resin paint) It is useful as a raw material, a resin modifier for polyester resins and epoxy resins.
  • a reaction in which an olefinic compound having a carbon-carbon double bond is converted to an aldehyde by reacting with carbon monoxide and hydrogen in the presence of a rhodium catalyst composed of a rhodium compound and a phosphorus compound is called a hydroformylation reaction.
  • the method for producing aldehydes using aldehyde has high industrial value.
  • a hydroformylation reaction of a compound having an ethylenic double bond at the molecular end produces a linear aldehyde and a branched aldehyde.
  • an isomer in which the double bond is isomerized and an aldehyde in which the isomer is hydroformylated are by-produced.
  • the catalytic activity in the hydroformylation reaction, the linear aldehyde selectivity, and the production ratio of the linear aldehyde to the branched aldehyde are, for example, the reaction temperature, the composition ratio of the mixed gas composed of carbon monoxide and hydrogen, the pressure of the mixed gas, It varies depending on various hydroformylation reaction conditions such as the type and amount of the solvent used, the structure of the terminal olefin compound, and the type of phosphorus compound constituting the rhodium catalyst.
  • the type of phosphorus compound constituting the rhodium catalyst greatly changes the electronic state of the rhodium atom as the central metal of the rhodium catalyst and the three-dimensional structure around the rhodium central metal in the rhodium complex intermediate that is the true active species of the rhodium catalyst.
  • the catalyst activity, the linear aldehyde selectivity, and the production ratio of the linear aldehyde to the branched aldehyde are greatly affected (see Non-Patent Documents 1 and 2).
  • Rhodium is expensive, and in order to carry out the hydroformylation reaction industrially advantageously, it reduces the amount of rhodium used by improving the catalytic activity, improves the aldehyde selectivity, and produces linear and branched aldehydes. Simultaneously controlling the ratio to the desired range is important in reducing the aldehyde factory manufacturing costs, and various bisphosphites have been developed and reported to achieve this goal.
  • a linear dialdehyde is produced by hydroformylating a linear olefinic compound having an ethylenic double bond and an aldehyde group at the molecular terminal (hereinafter sometimes referred to as a linear unsaturated aldehyde). How to do is known.
  • Patent Document 1 discloses the stability of bisphosphite. Specifically, 100 mg (0.102 mmol) of bisphosphite A is added to 100 ml of toluene containing 70 ppm of water (0.337 mmol as water) (conditions in which 3.3 moles of water is present relative to bisphosphite A). ), When treated at 125 ° C. in a nitrogen atmosphere, it is shown that the residual rate of bisphosphite A after 3 hours is 70%.
  • the amount of rhodium used per 1 kg of 7-octen-1-al is 0.025 mmol in terms of rhodium atoms, and from the viewpoint of reducing catalyst costs in the production cost of dialdehyde, There is room for improvement.
  • water and / or carboxylic acid may be contained in a linear unsaturated aldehyde such as 7-octen-1-al used as a raw material. In such a case, it is considered that sufficient reaction results cannot be obtained from the stability of bisphosphite A disclosed in Patent Document 1, and it can be said that there is still room for improvement.
  • the inventors reduce the reaction pressure of a mixed gas composed of carbon monoxide and hydrogen as the reaction proceeds, for example, Surprisingly, the conventional disclosure is achieved by controlling the reaction pressure of the mixed gas composed of carbon monoxide and hydrogen to be 30 to 80% of the pressure at the start of the reaction when the conversion rate exceeds 70%. It has been found that the catalytic activity can be maintained even when the rhodium is used in a smaller amount than the conventional method, and the dialdehyde selectivity and the production ratio of linear dialdehyde to branched dialdehyde can be controlled. Further, the present inventors have found that the same reaction results can be achieved even when the reaction solution contains water and / or carboxylic acid up to a certain range at the start of the reaction, and have further studied to complete the present invention.
  • R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
  • W represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 5 to 18 carbon atoms, or Represents an alkylene-arylene group having 7 to 11 carbon atoms.
  • a rhodium catalyst comprising a bisphosphite (hereinafter referred to as bisphosphite (I)) and a rhodium compound, a linear olefin having an ethylenic double bond and an aldehyde group at each molecular end, respectively.
  • a method for producing a dialdehyde by reacting a functional compound (linear unsaturated aldehyde) with carbon monoxide and hydrogen, the reaction pressure of a mixed gas composed of carbon monoxide and hydrogen is reduced as the reaction proceeds.
  • a method for producing a dialdehyde characterized in that [2] The water content in the reaction solution at the start of the reaction is 0.1 to 500 mmol / kg, and the carboxylic acid content in the reaction solution is 0.1 to 50 mmol / kg as carboxyl groups.
  • the linear unsaturated aldehyde is 5-hexen-1-al, 6-hepten-1-al, 7-octen-1-al, 8-nonen-1-al, 9-decene-1-al, 10
  • the reaction temperature is 50 to 130 ° C.
  • the pressure at the start of the reaction is 0
  • generation ratio of a linear dialdehyde and a branched dialdehyde is 80 / 20-90 / 10 can be manufactured industrially advantageously with the rhodium usage-amount reduced conventionally.
  • the rhodium catalyst is formed in a reaction system by supplying a solution in which a rhodium compound is dissolved in a solvent and a solution in which bisphosphite (I) is dissolved in a solvent, respectively, to the hydroformylation reaction system.
  • a rhodium compound and bisphosphite (I) are dissolved in a solvent under an inert gas atmosphere, and then a rhodium catalyst solution is prepared separately by stirring in a mixed gas atmosphere preferably consisting of carbon monoxide and hydrogen.
  • the rhodium catalyst solution may be supplied to the hydroformylation reaction system. From the viewpoint of sufficiently expressing the catalytic activity, a method of separately preparing a rhodium catalyst solution and then supplying it to the hydroformylation reaction system is preferable.
  • rhodium compounds examples include Rh (NO 3 ) 2 , Rh (OAc) 2 , Rh (acac) (CO) 2 , Rh (acac) (CO) (PPh 3 ).
  • Rh (acac) (CO) 2 is preferably used from the viewpoint that a rhodium catalyst
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.
  • Examples of the alkoxy group 4 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group. Of these, an alkyl group having 1 to 4 carbon atoms is preferable, and a t-butyl group is more preferable.
  • alkylene group having 1 to 20 carbon atoms represented by W examples include, for example, a methylene group, 1,2-ethylene group, 1,2-dimethylethylene group, 1,2-propylene group, 2-methyl-1,2-propylene group. 1,3-propylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 1,2-dimethyl-1,3-propylene group, 2,2-dimethyl-1 , 3-propylene group, 1,4-butylene group, 2,4-pentylene group, hexamethylene group, octamethylene group, tetramethylethylene group, tetramethylene group, etc., and a cycloalkylene group having 5 to 18 carbon atoms
  • alkylene groups having 2 to 5 carbon atoms are preferable, and 1,2-ethylene group, 1,2-dimethylethylene group, 1,2-propylene group, 2-methyl-1,2-propylene group, 1,3 -Propylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 1,2-dimethyl-1,3-propylene group, 2,2-dimethyl-1,3-propylene And more preferably a 1,4-butylene group.
  • the solvent that can be used for the preparation of the rhodium catalyst is preferably an aprotic solvent from the viewpoint of suppressing hydrolysis of bisphosphite (I), and is a reaction that coexists in the hydroformylation reaction as necessary from the viewpoint of recovering and utilizing the solvent. It is preferable that it is the same kind of solvent as an inert solvent.
  • solvents examples include saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, and cyclohexane; benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, o-xylene, m-xylene, and p-xylene.
  • Aromatic hydrocarbons such as o-ethyltoluene, m-ethyltoluene, p-ethyltoluene; alcohols such as isopropanol, isobutanol and neopentyl alcohol; diethyl ether, dipropyl ether, butyl methyl ether, t-butyl methyl ether , Ethers such as dibutyl ether, ethyl phenyl ether, diphenyl ether, tetrahydrofuran, 1,4-dioxane; acetone, ethyl methyl ketone, methyl propyl ketone, diethyl ketone, ethyl Piruketon, etc.
  • ketones such as dipropyl ketone.
  • These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the rhodium catalyst solution is preferably prepared batch-wise or semi-batch-wise using a complete mixing tank reactor.
  • the rhodium catalyst solution is preferably prepared in an inert gas atmosphere such as nitrogen, argon, or helium, and nitrogen is preferably used in terms of industrial availability and cost.
  • the pressure of the inert gas is not particularly limited, but usually normal pressure to 0.5 MPa (gauge pressure) is preferable.
  • the amount of bisphosphite (I) used is preferably 1 to 100 moles, more preferably 2 to 20 moles, relative to the rhodium atom. Within this range, both catalytic activity and dialdehyde selectivity are improved, and the effects of the present invention are further exhibited.
  • the temperature at which the rhodium catalyst used in the production method of the present invention is prepared is preferably 10 to 80 ° C, more preferably 20 to 50 ° C.
  • the rhodium catalyst solution prepared in an inert gas atmosphere is preferably preliminarily placed in a mixed gas atmosphere composed of carbon monoxide and hydrogen before being supplied to the hydroformylation reaction system.
  • the pressure of the mixed gas composed of carbon monoxide and hydrogen is not particularly limited, but it is usually preferably from normal pressure to 0.5 MPa (gauge pressure).
  • the production method of the present invention can be carried out by introducing a rhodium catalyst as a solution into a linear unsaturated aldehyde in the presence of a mixed gas composed of carbon monoxide and hydrogen.
  • the production method of the present invention can be carried out batch-wise or semi-batch-wise using a complete mixing tank reactor, and is also a complete mixing tank reactor or tube reactor, and further comprises 2 to 3 of these. You may implement by a continuous flow type using what was connected in series.
  • the effect of the present invention that is, the catalytic activity is improved and the dialdehyde is increased, by increasing the dissolution rate of the mixed gas composed of carbon monoxide and hydrogen in the linear unsaturated aldehyde in which the rhodium catalyst is dissolved. It is preferable from the viewpoint of achieving both improvement in selectivity.
  • the mixed gas may be continuously supplied from the bottom of the reactor, or an ejector having a mixing chamber.
  • a loop venturi reactor may be used as a tubular reactor equipped with
  • linear unsaturated aldehydes examples include 5-hexen-1-al, 6-hepten-1-al, 7-octen-1-al, 8-nonen-1-al, 9-decene-1-al, 10 -Undecen-1-al, 11-dodesen-1-al and the like.
  • the effect of the invention is remarkable when 7-octen-1-al is used.
  • 7-octen-1-al having a purity of 95% by mass or more can also be used.
  • 7-octen-1-al can be produced, for example, by isomerizing 2,7-octadien-1-ol in the presence of a copper-based catalyst.
  • the 7-octen-1-al produced in this way includes 1-octanal, 7-octen-1-ol, trans-6-octen-1-al, cis-6-octen-1-al and the like. Included as product. Since these by-products do not significantly poison the rhodium catalyst used in the production method of the present invention, it is possible to hydroformylate 7-octen-1-al while containing these impurities. . That is, the scope of the invention is not limited by the purity of the linear unsaturated aldehyde.
  • the water content in the reaction solution at the start of the reaction is 0.1 to 500 mmol / kg, and the carboxylic acid content in the reaction solution is 0.1 to 50 mmol / kg as carboxyl groups. Even if the reaction is carried out in kg, the reaction proceeds well.
  • the water content in the reaction solution at the start of the reaction is preferably 0.1 to 50 mmol / kg.
  • the content of carboxylic acid in the reaction solution is preferably 0.1 to 25 mmol / kg as carboxyl groups.
  • the linear unsaturated aldehyde used as a raw material in the production method of the present invention may contain water and / or carboxylic acid.
  • the production method of the present invention may be performed in the presence of a solvent.
  • a solvent include the same solvents as those described above that can be used when preparing a rhodium catalyst solution.
  • the amount used is preferably from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, based on the entire reaction solution.
  • the usage-amount of a solvent means the sum total of the solvent supplied as a solution of a rhodium catalyst, and the solvent supplied separately to a reaction system.
  • the amount of rhodium used in the reaction solution is preferably 1.0 ⁇ 10 ⁇ 4 to 6.0 ⁇ 10 ⁇ 1 mmol / kg as rhodium atoms, and 1.0 ⁇ 10 ⁇ It is more preferably 3 to 2.5 ⁇ 10 ⁇ 1 mmol / kg, and further preferably 1.0 ⁇ 10 ⁇ 3 to 2.5 ⁇ 10 ⁇ 2 mmol / kg.
  • the amount of bisphosphite (I) used in the reaction solution is preferably 1 to 100 mol times, more preferably 2 to 20 mol times relative to the rhodium atom. In these ranges, high catalytic activity and high dialdehyde selectivity can be achieved.
  • the reaction temperature is preferably 50 to 130 ° C, more preferably 100 to 120 ° C.
  • the reaction temperature is within the above range, high catalyst activity and high dialdehyde selectivity can be achieved without decomposition of the rhodium catalyst.
  • the range of 0.5 / 1 to 5/1 is preferable, and 1/1 to 3/1 is more preferable.
  • the pressure during the reaction of such a mixed gas is preferably 0.5 to 10.0 MPa (gauge pressure), more preferably 1.0 to 5.0 MPa (gauge pressure).
  • a feature of the production method of the present invention is that a hydroformylation reaction of a linear unsaturated aldehyde is carried out by setting a mixed gas pressure composed of carbon monoxide and hydrogen at the start of the reaction to a relatively high value.
  • the reaction pressure of the mixed gas composed of carbon monoxide and hydrogen is reduced.
  • the reaction pressure of the mixed gas composed of carbon monoxide and hydrogen is reacted stepwise or continuously. The reaction is carried out while controlling the pressure to be 30 to 80%, preferably 40 to 70% of the starting pressure.
  • the production method of the present invention for example, when a batch-type or semi-batch-type reactor is used, in the stage where the conversion rate of the linear unsaturated aldehyde exceeds 70%, mixing of carbon monoxide and hydrogen is performed.
  • the reaction is further carried out by controlling the reaction pressure of the gas stepwise or continuously so that it is 30 to 80%, preferably 40 to 70% of the pressure at the start of the reaction.
  • a plurality of batch reactors are connected, and the reaction is performed in the first reactor until the conversion rate of the linear unsaturated aldehyde exceeds 70%, and then the reaction solution in the first reactor is mixed with carbon monoxide and hydrogen.
  • the reaction may be carried out in a continuous flow type reaction system having a step of transferring to a second reactor where the reaction pressure of the mixed gas is 30 to 80% of that of the first reactor and continuing the reaction.
  • the reaction pressure of the mixed gas is 30 to 80% of that of the first reactor and continuing the reaction.
  • phosphorus compounds other than bisphosphite (I) as needed.
  • phosphorus compounds include triisopropylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tribenzylphosphine, triphenylphosphine, tris (p-methoxyphenyl) phosphine, tris (pN, N— Dimethylaminophenyl) phosphine, tris (p-fluorophenyl) phosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris (pentafluorophenyl) phosphine, bis (pentafluorophenyl) Phenylphosphine, diphenyl (pentafluorophenyl) phosphine, methyldiphen
  • a nitrogen-containing compound may further coexist as necessary.
  • nitrogen-containing compounds include triethylamine, tributylamine, tri-n-octylamine, N, N, N ′, N′-tetramethyl-1,2-diaminoethane, N, N, N ′, N′-.
  • Examples include pyrrolidine, N-methylmorpholine, pyridine, picoline, lutidine, collidine, and quinoline.
  • the amount used is preferably 100 to 3000 mol times, more preferably 500 to 2000 mol times with respect to the rhodium atom.
  • the reaction solution is left as it is without performing the operation of recovering rhodium from the reaction solution. It can be used directly in the next reaction such as a hydrogenation reaction or a reductive amination reaction.
  • a step of purifying the dialdehyde from the reaction solution by separating it from the rhodium catalyst component may be performed. There is no particular limitation on the method for separating and purifying dialdehyde from the reaction solution, and a known method can be applied.
  • low-boiling components can be distilled off from the hydroformylation reaction solution under reduced pressure, and the residue can be further purified by distillation to separate it into a distillation residue containing unreacted raw materials, dialdehyde and rhodium catalyst. You may reuse an unreacted raw material and distillation residue for the manufacturing method of this invention.
  • the constituents of the rhodium catalyst may be separated by subjecting the residue to methods such as evaporation, extraction, and adsorption.
  • Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by this Example and comparative example.
  • the 7-octen-1-al used as a raw material in each example and reference example has a purity of 95.4% by mass, and the main impurities are 1-octanal, trans-6-octen-1-al, cis-6- Octen-1-al.
  • the rhodium catalyst was prepared at room temperature, normal pressure, and nitrogen atmosphere, and the raw materials and solvent were previously purified by distillation and purged with nitrogen.
  • Bisphosphite has the following chemical formula
  • the compound shown in was used. These were synthesized according to known methods.
  • the amount of 7-octen-1-al consumed in the reaction solution (conversion rate), the amount of 1,9-nonanedial, 2-methyl-1,8-octanedial, and other products as the target products are Analysis and quantification by gas chromatography.
  • a mixed gas of carbon monoxide / hydrogen 1/1 (molar ratio) inside an autoclave having an internal volume of 3 L equipped with a Max blend blade, a rhodium catalyst solution inlet, a gas inlet, a gas outlet, and a sampling port
  • 717.00 g of 7-octen-1-al purity 95.4% by mass
  • 5.70 g (316.41 mmol) of water and 2.20 g (15.26 mmol) of octanoic acid were charged. It is.
  • the reaction was started at 5.0 MPa (gauge pressure).
  • the rhodium concentration in the reaction solution at the start of the reaction was 0.0115 mmol / kg as rhodium atoms
  • the amount of bisphosphite used was 6.72 mol times the rhodium atoms
  • the water content was 430 mmol / kg.
  • the carboxylic acid content was 20.88 mmol / kg as a carboxyl group.
  • the conversion rate of 7-octen-1-al after 8 hours of reaction was 85.2% when the time when the internal temperature of the reaction solution reached 120 ° C.
  • Example 2 In Example 1, the reaction was carried out in the same manner as in Example 1 except that water and octanoic acid were not charged.
  • the rhodium concentration in the reaction solution at the start of the reaction was 0.0116 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.72 mol times the rhodium atoms.
  • Example 3 In Example 1, 15.8 mg (0.061 mmol) was used instead of 29.2 mg (0.113 mmol) of Rh (acac) (CO) 2 and 744.7 mg (0.759 mmol) of bisphosphite A was used. 401.7 mg (0.409 mmol) is used instead of mmol), water and octanoic acid are not charged, and carbon monoxide / hydrogen inside the autoclave is 1/1 (molar ratio) up to 12 hours from the start of the reaction.
  • the reaction was carried out in the same manner as in Example 1 except that the reaction was performed for 6 hours (the total reaction time was 18 hours).
  • the rhodium concentration in the reaction solution at the start of the reaction was 0.0063 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.7 mol times the rhodium atoms.
  • the selectivity for isomers and the like was 10.6%.
  • the reaction was carried out in the same manner as in Example 1 except that the reaction was continued for 4 hours (the total reaction time was 12 hours).
  • the rhodium concentration in the reaction solution at the start of the reaction was 0.0134 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.7 mol times the rhodium atoms.
  • the selectivity for isomers and the like was 7.8%.
  • 5.0 MPa gauge pressure
  • the reaction was carried out in the same manner as in Example 1 except that the pressure was reduced to (gauge pressure) and further reacted for 4 hours (total reaction time was 12 hours).
  • the rhodium concentration in the reaction solution at the start of the reaction was 0.0189 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.72 mol times the rhodium atoms.
  • the selectivity for isomers and the like was 7.8%.
  • Example 1 Comparison with Examples 1 and 2)
  • 33.4 mg (0.130 mmol) was used instead of 29.2 mg (0.113 mmol) of Rh (acac) (CO) 2
  • 744.7 mg (0. 30 mmol) of bisphosphite A was used.
  • 759 mmol) is used instead of 851.7 mg (0.868 mmol)
  • the reaction was performed in the same manner as in Example 1 except that the reaction was performed for 12 hours at a constant 0.0 MPa (gauge pressure).
  • the rhodium concentration in the reaction solution at the start of the reaction was 0.0134 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.67 mol times the rhodium atoms.
  • Example 2 Comparison with Example 3
  • 17.7 mg (0.069 mmol) was used instead of 29.2 mg (0.113 mmol) of Rh (acac) (CO) 2
  • 744.7 mg (0.009 mmol) of bisphosphite A was used.
  • 759 mmol) is used instead of 451.0 mg (0.460 mmol)
  • the reaction was performed in the same manner as in Example 1 except that the reaction was performed for 18 hours at a constant 0.0 MPa (gauge pressure).
  • the rhodium concentration in the reaction solution at the start of the reaction was 0.0071 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.67 mol times the rhodium atoms.
  • Example 1 the water content in the reaction solution at the start of the reaction is 430 mmol / kg, and the carboxylic acid content is 20.88 mmol / kg as a carboxyl group. That is, 7-octen-1-al is hydroformylated with bisphosphite A in the presence of 5600 mole times or more of water and 260 mole times or more of octanoic acid. From the result of the residual rate test at 125 ° C. when 100 mg of bisphosphite is added to 100 ml of toluene having a water content of 70 ppm shown in Patent Document 1, the stability of bisphosphite is low and it is difficult to function as a catalyst.
  • the reaction proceeds well as shown in Example 1. That is, the water content in the reaction solution at the start of the reaction is 0.1 to 500 mmol / kg, and the carboxylic acid content in the reaction solution is 0.1 to 50 mmol / kg as carboxyl groups.
  • the production method of the present invention can be carried out satisfactorily.
  • Example 2 From Example 2 and Reference Example 1, the amount of rhodium used (in terms of concentration as rhodium atoms in the reaction solution at the start of the reaction) when dialdehyde is obtained in a yield of 89.4% by reaction for 12 hours is as shown in Example 2. Is 0.0116 mmol / kg, whereas in Reference Example 1, it is 0.0134 mmol / kg. That is, it can be seen that Example 2 to which the production method of the present invention that reduces the reaction pressure as the reaction progresses can reduce the amount of rhodium used by about 13% compared to Reference Example 1 in which the reaction pressure is maintained at a constant pressure. .
  • Example 3 the amount of rhodium used (in terms of the concentration of rhodium atoms in the reaction solution at the start of the reaction) when dialdehyde is obtained in a yield of 86.3% after 18 hours of reaction is In Example 3, it is 0.0063 mmol / kg, while in Reference Example 2, it is 0.0071 mmol / kg. That is, it can be seen that Example 3 to which the production method of the present invention is applied can reduce the amount of rhodium used by about 11% compared to Reference Example 2 in which the reaction pressure is maintained at a constant pressure.
  • the production method of the present invention in which the reaction pressure is reduced as the reaction proceeds, preferably, the linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular end, respectively.
  • the conversion rate exceeds 70%
  • the amount of rhodium used can be reduced by controlling the pressure to be 30 to 80% of the pressure at the start of the reaction stepwise or continuously. It turns out that it contributes to reduction. From Examples 4 and 5, it can be seen that the production method of the present invention can also be effectively carried out with bisphosphites B and C.
  • a dialdehyde having a production ratio of linear dialdehyde to branched dialdehyde of 80/20 to 90/10 can be advantageously produced industrially.
  • a diol mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol is obtained.
  • a diol mixture is a raw material for production such as polycarbonate, polyester, polyurethane, paint (polyester paint, Epoxy resin paint) It is useful as a raw material, a resin modifier for polyester resins and epoxy resins.

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Abstract

Provided is an industrially advantageous method for producing dialdehyde having a linear dialdehyde and branched dialdehyde production ratio of 80/20-90/10 using a smaller amount of rhodium than in the past. Specifically, provided is a method for producing dialdehyde by reacting linear olefinic compounds, each of which has an ethylenic double bond and an aldehyde group at the end of the molecule, with hydrogen and carbon monoxide in the presence of a rhodium catalyst comprising a bisphosphite shown by general formula (I) (in the formula, R represents a hydrogen atom, a C1-4 alkyl group, or a C1-4 alkoxy group, W represents a C1-20 alkylene group, a C5-18 cycloalkylene group, or a C7-11 alkylene-arylene group) and a rhodium compound, wherein the reaction pressure of a mixed gas comprising hydrogen and carbon monoxide is lowered as the reaction advances.

Description

ジアルデヒドの製造方法Method for producing dialdehyde
　本発明は、ジアルデヒドの製造方法に関する。詳細には、本発明は、各々の分子末端にエチレン性二重結合およびアルデヒド基をそれぞれ有する直鎖状オレフィン性化合物をヒドロホルミル化して直鎖状ジアルデヒド含有率が８０～９０質量％であるジアルデヒドを工業的に有利に製造する方法に関する。本発明の方法は、例えば、７－オクテン－１－アールから、１，９－ノナンジオールと２－メチル－１，８－オクタンジオールのジオール混合物（１，９－ノナンジオールの含有量８０～９０質量％）の合成中間体となる、１，９－ノナンジアール／２－メチル－１，８－オクタンジアールのジアルデヒド混合物の製造方法として有用である。前記１，９－ノナンジオールと２－メチル－１，８－オクタンジオールのジオール混合物は株式会社クラレより商品名「ＮＤ１５」として市販され、ポリカーボネート、ポリエステル、ポリウレタンなどの製造原料、塗料（ポリエステル塗料、エポキシ樹脂塗料）原料、ポリエステル樹脂やエポキシ樹脂の樹脂改質剤などとして有用である。 The present invention relates to a method for producing dialdehyde. More specifically, the present invention relates to a dihydroxy compound having a linear dialdehyde content of 80 to 90% by mass by hydroformylating a linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular end. The present invention relates to a method for producing an aldehyde industrially advantageously. The method of the present invention is, for example, from 7-octen-1-al to a diol mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol (content of 1,9-nonanediol of 80 to 90). It is useful as a method for producing a 1,9-nonane dial / 2-methyl-1,8-octane dial dialdehyde mixture which is a synthetic intermediate of (mass%). The diol mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol is commercially available from Kuraray Co., Ltd. under the trade name “ND15”, and is a raw material for producing polycarbonate, polyester, polyurethane and the like, paint (polyester paint, Epoxy resin paint) It is useful as a raw material, a resin modifier for polyester resins and epoxy resins.
　炭素－炭素二重結合を有するオレフィン性化合物を、ロジウム化合物とリン化合物からなるロジウム触媒の存在下、一酸化炭素および水素と反応させてアルデヒドに変換する反応はヒドロホルミル化反応と称され、この反応を利用したアルデヒドの製造方法は工業的価値が高い。 A reaction in which an olefinic compound having a carbon-carbon double bond is converted to an aldehyde by reacting with carbon monoxide and hydrogen in the presence of a rhodium catalyst composed of a rhodium compound and a phosphorus compound is called a hydroformylation reaction. The method for producing aldehydes using aldehyde has high industrial value.
　分子末端にエチレン性二重結合を有する化合物をヒドロホルミル化反応することにより、直鎖状アルデヒドと分岐状アルデヒドが生じる。なお、場合によっては、二重結合が異性化した異性体、この異性体がヒドロホルミル化されたアルデヒドが副生する。 A hydroformylation reaction of a compound having an ethylenic double bond at the molecular end produces a linear aldehyde and a branched aldehyde. In some cases, an isomer in which the double bond is isomerized and an aldehyde in which the isomer is hydroformylated are by-produced.
　ヒドロホルミル化反応における触媒活性、直鎖状アルデヒド選択率、および直鎖状アルデヒドと分岐状アルデヒドの生成比は、例えば反応温度、一酸化炭素および水素からなる混合ガスの組成比、混合ガスの圧力、溶媒の種類および使用量、末端オレフィン化合物の構造、ロジウム触媒を構成するリン化合物の種類などのヒドロホルミル化の反応諸条件で変化する。とりわけ、ロジウム触媒を構成するリン化合物の種類は、ロジウム触媒の中心金属たるロジウム原子の電子状態およびロジウム触媒の真の活性種であるロジウム錯体中間体におけるロジウム中心金属周りの立体構造を大きく変化させることから、触媒活性、直鎖状アルデヒド選択率および直鎖状アルデヒドと分岐状アルデヒドの生成比への影響が大きいことが知られている（非特許文献１～２参照）。 The catalytic activity in the hydroformylation reaction, the linear aldehyde selectivity, and the production ratio of the linear aldehyde to the branched aldehyde are, for example, the reaction temperature, the composition ratio of the mixed gas composed of carbon monoxide and hydrogen, the pressure of the mixed gas, It varies depending on various hydroformylation reaction conditions such as the type and amount of the solvent used, the structure of the terminal olefin compound, and the type of phosphorus compound constituting the rhodium catalyst. In particular, the type of phosphorus compound constituting the rhodium catalyst greatly changes the electronic state of the rhodium atom as the central metal of the rhodium catalyst and the three-dimensional structure around the rhodium central metal in the rhodium complex intermediate that is the true active species of the rhodium catalyst. Thus, it is known that the catalyst activity, the linear aldehyde selectivity, and the production ratio of the linear aldehyde to the branched aldehyde are greatly affected (see Non-Patent Documents 1 and 2).
　ロジウムは高価であり、ヒドロホルミル化反応を工業的に有利に実施するために、触媒活性を向上させることによるロジウム使用量の低減、アルデヒド選択率の向上、および直鎖状アルデヒドと分岐状アルデヒドの生成比を所望の範囲に制御すること、を同時に達成することがアルデヒドの工場製造原価を低減するうえで重要であり、かかる目的の達成のために様々なビスホスファイトが開発され報告されている。 Rhodium is expensive, and in order to carry out the hydroformylation reaction industrially advantageously, it reduces the amount of rhodium used by improving the catalytic activity, improves the aldehyde selectivity, and produces linear and branched aldehydes. Simultaneously controlling the ratio to the desired range is important in reducing the aldehyde factory manufacturing costs, and various bisphosphites have been developed and reported to achieve this goal.
　一方、分子末端にエチレン性二重結合およびアルデヒド基を各々有する直鎖状オレフィン性化合物（以下、直鎖不飽和アルデヒドと称する場合がある。）をヒドロホルミル化することによって直鎖状ジアルデヒドを製造する方法が知られている。
　例えば、特定構造のビスホスファイト、典型的には以下に示すビスホスファイトＡ、ビスホスファイトＢ、ビスホスファイトＣなどを用いた７－オクテン－１－アールのヒドロホルミル化反応において、直鎖状ジアルデヒド（１，９－ノナンジアール；以下ＮＬと略称する）および分岐状ジアルデヒド（２－メチル－１，８－オクタンジアール；以下ＭＯＬと略称する）の生成比およびジアルデヒド選択率が開示されている（特許文献１参照）。
　具体的には、ビスホスファイトＡを用いる場合には、ＮＬ／ＭＯＬ＝８５．１／１４．９のジアルデヒドが選択率９７．０％で、同一条件でビスホスファイトＢを用いる場合には、ＮＬ／ＭＯＬ＝７９．８／２１．２のジアルデヒドが選択率９７．０％で、同一条件でビスホスファイトＣを用いる場合には、ＮＬ／ＭＯＬ＝７９．７／２０．３のジアルデヒドが選択率９７．７％で得られることが示されている。 On the other hand, a linear dialdehyde is produced by hydroformylating a linear olefinic compound having an ethylenic double bond and an aldehyde group at the molecular terminal (hereinafter sometimes referred to as a linear unsaturated aldehyde). How to do is known.
For example, in the hydroformylation reaction of 7-octen-1-al using a bisphosphite having a specific structure, typically bisphosphite A, bisphosphite B, bisphosphite C and the like shown below, Disclosed are the production ratio and dialdehyde selectivity of dialdehyde (1,9-nonane dial; hereinafter abbreviated as NL) and branched dialdehyde (2-methyl-1,8-octane dial; hereinafter abbreviated as MOL). (See Patent Document 1).
Specifically, when bisphosphite A is used, the dialdehyde having NL / MOL = 85.1 / 14.9 has a selectivity of 97.0% and bisphosphite B is used under the same conditions. When the dialdehyde having NL / MOL = 79.8 / 21.2 has a selectivity of 97.0% and bisphosphite C is used under the same conditions, the dialdehyde having NL / MOL = 79.7 / 20.3 It has been shown that the aldehyde is obtained with a selectivity of 97.7%.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　また、特許文献１にはビスホスファイトの安定性について開示されている。具体的には、水７０ｐｐｍを含むトルエン１００ｍｌ（水として０．３３７ミリモル）にビスホスファイトＡ　１００ｍｇ（０．１０２ミリモル）を加え（ビスホスファイトＡに対し水が３．３モル倍存在する条件）、窒素雰囲気下で１２５℃処理した場合、３時間後のビスホスファイトＡの残存率が７０％であることが示されている。 Patent Document 1 discloses the stability of bisphosphite. Specifically, 100 mg (0.102 mmol) of bisphosphite A is added to 100 ml of toluene containing 70 ppm of water (0.337 mmol as water) (conditions in which 3.3 moles of water is present relative to bisphosphite A). ), When treated at 125 ° C. in a nitrogen atmosphere, it is shown that the residual rate of bisphosphite A after 3 hours is 70%.
特開２００８－３１１２５号公報JP 2008-31125 A
　特許文献１の実施例においては、７－オクテン－１－アール１ｋｇに対するロジウム使用量はロジウム原子換算で０．０２５ミリモルであり、ジアルデヒドの製造原価に占める触媒費用の削減の観点からは、なお改良の余地がある。
　一方、工業的な観点からは、原料として用いる７－オクテン－１－アールのような直鎖不飽和アルデヒドに水および／またはカルボン酸が含有されていることがある。かかる場合には、特許文献１に開示されているビスホスファイトＡの安定性からは、十分な反応成績が得られないと考えられ、なお改良の余地があるといえる。 In the examples of Patent Document 1, the amount of rhodium used per 1 kg of 7-octen-1-al is 0.025 mmol in terms of rhodium atoms, and from the viewpoint of reducing catalyst costs in the production cost of dialdehyde, There is room for improvement.
On the other hand, from an industrial viewpoint, water and / or carboxylic acid may be contained in a linear unsaturated aldehyde such as 7-octen-1-al used as a raw material. In such a case, it is considered that sufficient reaction results cannot be obtained from the stability of bisphosphite A disclosed in Patent Document 1, and it can be said that there is still room for improvement.
　本発明者らは、直鎖不飽和アルデヒド、とりわけ７－オクテン－１－アールのヒドロホルミル化反応において、反応の進行に伴って一酸化炭素および水素からなる混合ガスの反応圧力を低下させること、例えば転化率が７０％を超えた段階において、一酸化炭素および水素からなる混合ガスの反応圧力を反応開始時の圧力の３０～８０％となるように制御することによって、意外なことに、従来開示されている方法よりも少ないロジウム使用量であっても触媒活性を維持することが可能であり、ジアルデヒド選択率および直鎖状ジアルデヒドと分岐状ジアルデヒドの生成比も制御できることを見出した。また、反応開始時に反応液が一定範囲の量まで水および／またはカルボン酸を含有している場合でも同等の反応成績が達成できることを見出し、さらに検討して本発明を完成した。 In the hydroformylation reaction of a linear unsaturated aldehyde, especially 7-octen-1-al, the inventors reduce the reaction pressure of a mixed gas composed of carbon monoxide and hydrogen as the reaction proceeds, for example, Surprisingly, the conventional disclosure is achieved by controlling the reaction pressure of the mixed gas composed of carbon monoxide and hydrogen to be 30 to 80% of the pressure at the start of the reaction when the conversion rate exceeds 70%. It has been found that the catalytic activity can be maintained even when the rhodium is used in a smaller amount than the conventional method, and the dialdehyde selectivity and the production ratio of linear dialdehyde to branched dialdehyde can be controlled. Further, the present inventors have found that the same reaction results can be achieved even when the reaction solution contains water and / or carboxylic acid up to a certain range at the start of the reaction, and have further studied to complete the present invention.
　すなわち本発明は、
［１］一般式（Ｉ） That is, the present invention
[1] General formula (I)
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
（式中、Ｒは水素原子、炭素数１～４のアルキル基または炭素数１～４のアルコキシ基を表し、Ｗは炭素数１～２０のアルキレン基、炭素数５～１８のシクロアルキレン基または炭素数７～１１のアルキレン－アリーレン基を表す。）
で示されるビスホスファイト（以下、ビスホスファイト（Ｉ）と称する。）およびロジウム化合物からなるロジウム触媒の存在下、各々の分子末端にエチレン性二重結合およびアルデヒド基をそれぞれ有する直鎖状オレフィン性化合物（直鎖不飽和アルデヒド）を、一酸化炭素および水素と反応させてジアルデヒドを製造する方法において、反応の進行に伴って、一酸化炭素および水素からなる混合ガスの反応圧力を低下させることを特徴とするジアルデヒドの製造方法；
［２］反応開始時の反応液中の含水量が０．１～５００ミリモル／ｋｇでありかつ反応液中のカルボン酸の含有量がカルボキシル基として０．１～５０ミリモル／ｋｇであることを特徴とする、［１］のジアルデヒドの製造方法；
［３］直鎖不飽和アルデヒドの転化率が７０％を超えた段階において、一酸化炭素および水素からなる混合ガスの反応圧力を段階的または連続的に反応開始時の圧力の３０～８０％となるように制御することを特徴とする［１］または［２］のジアルデヒドの製造方法；
［４］反応器を複数連結し、第１反応器において直鎖不飽和アルデヒドの転化率が７０％を超えるまで反応を行い、次いで第１反応器中の反応液を、一酸化炭素および水素からなる混合ガスの反応圧力が第１反応器の３０～８０％である第２反応器に移送し、引続き反応を行う工程を有することを特徴とする、［３］のジアルデヒドの製造方法；
［５］直鎖不飽和アルデヒドが５－ヘキセン－１－アール、６－ヘプテン－１－アール、７－オクテン－１－アール、８－ノネン－１－アール、９－デセン－１－アール、１０－ウンデセン－１－アール、１１－ドデセン－１－アールのいずれかである、［１］～［４］のいずれかのジアルデヒドの製造方法；
［６］一般式（Ｉ）において、Ｒが炭素数１～４のアルキル基または炭素数１～４のアルコキシ基であり、Ｗが炭素数１～２０のアルキレン基であるビスホスファイト（Ｉ）を用いることを特徴とする、［１］～［５］のいずれかのジアルデヒドの製造方法；
［７］Ｒがｔ－ブチル基であり、Ｗが炭素数２～５のアルキレン基であるビスホスファイト（Ｉ）を用いることを特徴とする、［６］のジアルデヒドの製造方法；および、
［８］反応液中のロジウム濃度がロジウム原子として１．０×１０－４～６．０×１０－１ミリモル／ｋｇであり、ビスホスファイトの使用量がロジウム原子に対して１～１００モル倍であり、反応温度が５０～１３０℃であり、一酸化炭素および水素の組成比がモル比として一酸化炭素／水素＝０．１／１～１０／１でかつ反応開始時の圧力が０．５～１０ＭＰａ（ゲージ圧）である、［１］～［７］のいずれかのジアルデヒドの製造方法；である。 (Wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, W represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 5 to 18 carbon atoms, or Represents an alkylene-arylene group having 7 to 11 carbon atoms.)
In the presence of a rhodium catalyst comprising a bisphosphite (hereinafter referred to as bisphosphite (I)) and a rhodium compound, a linear olefin having an ethylenic double bond and an aldehyde group at each molecular end, respectively. In a method for producing a dialdehyde by reacting a functional compound (linear unsaturated aldehyde) with carbon monoxide and hydrogen, the reaction pressure of a mixed gas composed of carbon monoxide and hydrogen is reduced as the reaction proceeds. A method for producing a dialdehyde, characterized in that
[2] The water content in the reaction solution at the start of the reaction is 0.1 to 500 mmol / kg, and the carboxylic acid content in the reaction solution is 0.1 to 50 mmol / kg as carboxyl groups. A method for producing a dialdehyde according to [1], characterized by:
[3] When the conversion rate of the linear unsaturated aldehyde exceeds 70%, the reaction pressure of the mixed gas composed of carbon monoxide and hydrogen is set to 30 to 80% of the pressure at the start of the reaction stepwise or continuously. The method for producing a dialdehyde according to [1] or [2], which is controlled so that
[4] A plurality of reactors are connected, and the reaction is performed in the first reactor until the conversion rate of the linear unsaturated aldehyde exceeds 70%, and then the reaction solution in the first reactor is converted from carbon monoxide and hydrogen. The method for producing a dialdehyde according to [3], further comprising a step of transferring the mixed gas to a second reactor having a reaction pressure of 30 to 80% of that of the first reactor and subsequently performing the reaction;
[5] The linear unsaturated aldehyde is 5-hexen-1-al, 6-hepten-1-al, 7-octen-1-al, 8-nonen-1-al, 9-decene-1-al, 10 A process for producing a dialdehyde according to any one of [1] to [4], which is any one of undecene-1-al and 11-dodecene-1-al;
[6] Bisphosphite (I) wherein R is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms and W is an alkylene group having 1 to 20 carbon atoms in the general formula (I) A process for producing a dialdehyde according to any one of [1] to [5], wherein
[7] A method for producing a dialdehyde according to [6], wherein bisphosphite (I) wherein R is a t-butyl group and W is an alkylene group having 2 to 5 carbon atoms is used; and
[8] The rhodium concentration in the reaction solution is 1.0 × 10 −4 to 6.0 × 10 −1 mmol / kg as rhodium atoms, and the amount of bisphosphite used is 1 to 100 mol with respect to rhodium atoms. The reaction temperature is 50 to 130 ° C., the composition ratio of carbon monoxide and hydrogen is carbon monoxide / hydrogen = 0.1 / 1 to 10/1 as a molar ratio, and the pressure at the start of the reaction is 0 The method for producing a dialdehyde according to any one of [1] to [7], which is 5 to 10 MPa (gauge pressure).
　本発明によれば、直鎖状ジアルデヒドと分岐状ジアルデヒドの生成比が８０／２０～９０／１０であるジアルデヒドを、従来よりも低減されたロジウム使用量で工業的に有利に製造できる。本発明の方法は、例えば、７－オクテン－１－アールから、１，９－ノナンジオールと２－メチル－１，８－オクタンジオールのジオール混合物（１，９－ノナンジオールの含有量８０～９０質量％）の合成中間体となる、１，９－ノナンジアール／２－メチル－１，８－オクタンジアール（ＮＬ／ＭＯＬ）のジアルデヒド混合物（ＮＬ／ＭＯＬ＝８０／２０～９０／１０）の製造方法として有用である。 ADVANTAGE OF THE INVENTION According to this invention, the dialdehyde whose production | generation ratio of a linear dialdehyde and a branched dialdehyde is 80 / 20-90 / 10 can be manufactured industrially advantageously with the rhodium usage-amount reduced conventionally. . The method of the present invention is, for example, from 7-octen-1-al to a diol mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol (content of 1,9-nonanediol of 80 to 90). (Mass%) of 1,9-nonanediar / 2-methyl-1,8-octanediar (NL / MOL) dialdehyde mixture (NL / MOL = 80/20 to 90/10) It is useful as a production method.
　以下、本発明の製造方法について詳細に説明する。 Hereinafter, the production method of the present invention will be described in detail.
　本発明の製造方法においては、ロジウム触媒はロジウム化合物を溶媒に溶解させた溶液およびビスホスファイト（Ｉ）を溶媒に溶解させた溶液をそれぞれヒドロホルミル化反応系に供給して反応系内で形成させても、または不活性ガス雰囲気下でロジウム化合物およびビスホスファイト（Ｉ）を溶媒に溶解させ、次いで好ましくは一酸化炭素および水素からなる混合ガス雰囲気下で撹拌してロジウム触媒の溶液を別途調製し、係るロジウム触媒の溶液をヒドロホルミル化反応系に供給してもよい。触媒活性を十分に発現させる観点からは、ロジウム触媒の溶液を別途調製した後、ヒドロホルミル化反応系に供給する方法が好ましい。 In the production method of the present invention, the rhodium catalyst is formed in a reaction system by supplying a solution in which a rhodium compound is dissolved in a solvent and a solution in which bisphosphite (I) is dissolved in a solvent, respectively, to the hydroformylation reaction system. Alternatively, a rhodium compound and bisphosphite (I) are dissolved in a solvent under an inert gas atmosphere, and then a rhodium catalyst solution is prepared separately by stirring in a mixed gas atmosphere preferably consisting of carbon monoxide and hydrogen. However, the rhodium catalyst solution may be supplied to the hydroformylation reaction system. From the viewpoint of sufficiently expressing the catalytic activity, a method of separately preparing a rhodium catalyst solution and then supplying it to the hydroformylation reaction system is preferable.
　本発明の製造方法で使用することができるロジウム化合物としては、例えば、Ｒｈ（ＮＯ３）２、Ｒｈ（ＯＡｃ）２、Ｒｈ（ａｃａｃ）（ＣＯ）２、Ｒｈ（ａｃａｃ）（ＣＯ）（ＰＰｈ３）、ＨＲｈ（ＣＯ）（ＰＰｈ３）３、ＲｈＣｌ（ＣＯ）（ＰＰｈ３）２、ＲｈＢｒ（ＣＯ）（ＰＰｈ３）２、ＲｈＣｌ（ＰＰｈ３）３、［Ｒｈ（μ－ＯＡｃ）（ＣＯ）２］２、［Ｒｈ（μ－ＯＡｃ）（ＣＯＤ）］２、［Ｒｈ（μ－Ｃｌ）（ＣＯＤ）］２、［Ｒｈ（μ－Ｃｌ）（ＣＯ）２］２、Ｒｈ４（ＣＯ）１２、Ｒｈ４（ＣＯ）８（ＰＰｈ３）４、Ｒｈ６（ＣＯ）１６、（なお、ＯＡｃはアセチル基、ａｃａｃはアセチルアセトナト基、Ｐｈはフェニル基、ＣＯＤは１，５－シクロオクタジエン、をそれぞれ表す）などが挙げられる。なかでも、一酸化炭素および水素からなる混合ガス雰囲気下で容易にロジウム触媒を調製できる観点から、Ｒｈ（ａｃａｃ）（ＣＯ）２を用いることが好ましい。 Examples of rhodium compounds that can be used in the production method of the present invention include Rh (NO 3 ) 2 , Rh (OAc) 2 , Rh (acac) (CO) 2 , Rh (acac) (CO) (PPh 3 ). ), HRh (CO) (PPh 3 ) 3 , RhCl (CO) (PPh 3 ) 2 , RhBr (CO) (PPh 3 ) 2 , RhCl (PPh 3 ) 3 , [Rh (μ-OAc) (CO) 2 ] 2 , [Rh (μ-OAc) (COD)] 2 , [Rh (μ-Cl) (COD)] 2 , [Rh (μ-Cl) (CO) 2 ] 2 , Rh 4 (CO) 12 , Rh 4 (CO) 8 (PPh 3 ) 4 , Rh 6 (CO) 16 , wherein OAc is an acetyl group, acac is an acetylacetonato group, Ph is a phenyl group, COD is 1,5-cyclooctadiene, Respectively) Etc., and the like. Among these, Rh (acac) (CO) 2 is preferably used from the viewpoint that a rhodium catalyst can be easily prepared in a mixed gas atmosphere composed of carbon monoxide and hydrogen.
　本発明の製造方法では、一般式（Ｉ） In the production method of the present invention, the general formula (I)
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（式中、ＲおよびＷは前記定義のとおりである。）
で示されるビスホスファイト（Ｉ）を、本発明の製造方法で用いるロジウム触媒を構成する成分として用いることが特徴である。 (Wherein R and W are as defined above.)
It is characterized by using the bisphosphite (I) shown by these as a component which comprises the rhodium catalyst used with the manufacturing method of this invention.
　Ｒが表す炭素数１～４のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基が挙げられ、炭素数１～４のアルコキシ基としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、ｓｅｃ－ブトキシ基、ｔ－ブトキシ基が挙げられる。中でも炭素数１～４のアルキル基が好ましく、ｔ－ブチル基であることがより好ましい。 Examples of the alkyl group having 1 to 4 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. Examples of the alkoxy group 4 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group. Of these, an alkyl group having 1 to 4 carbon atoms is preferable, and a t-butyl group is more preferable.
　Ｗが表す炭素数１～２０のアルキレン基としては、例えばメチレン基、１，２－エチレン基、１，２－ジメチルエチレン基、１，２－プロピレン基、２－メチル－１，２－プロピレン基、１，３－プロピレン基、１－メチル－１，３－プロピレン基、２－メチル－１，３－プロピレン基、１，２－ジメチル－１，３－プロピレン基、２，２－ジメチル－１，３－プロピレン基、１，４－ブチレン基、２，４－ペンチレン基、ヘキサメチレン基、オクタメチレン基、テトラメチルエチレン基、テトラメチレン基などが挙げられ、炭素数５～１８のシクロアルキレン基としては、例えばシクロプロピレン基、１，２－シクロペンチレン基、１，３－シクロペンチレン基、１，２－シクロヘキシレン基、１，３－シクロヘキシレン基、１，４－シクロヘキシレン基などが挙げられ、炭素数７～１１のアルキレン－アリーレン基としては、例えば置換基としてアルキル基（メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基）を有していてもよいベンジレン基などが挙げられる。これらの中でも炭素数２～５のアルキレン基が好ましく、１，２－エチレン基、１，２－ジメチルエチレン基、１，２－プロピレン基、２－メチル－１，２－プロピレン基、１，３－プロピレン基、１－メチル－１，３－プロピレン基、２－メチル－１，３－プロピレン基、１，２－ジメチル－１，３－プロピレン基、２，２－ジメチル－１，３－プロピレン基、１，４－ブチレン基であることがより好ましい。 Examples of the alkylene group having 1 to 20 carbon atoms represented by W include, for example, a methylene group, 1,2-ethylene group, 1,2-dimethylethylene group, 1,2-propylene group, 2-methyl-1,2-propylene group. 1,3-propylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 1,2-dimethyl-1,3-propylene group, 2,2-dimethyl-1 , 3-propylene group, 1,4-butylene group, 2,4-pentylene group, hexamethylene group, octamethylene group, tetramethylethylene group, tetramethylene group, etc., and a cycloalkylene group having 5 to 18 carbon atoms For example, cyclopropylene group, 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-silane Examples of the alkylene-arylene group having 7 to 11 carbon atoms include an alkyl group (methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec- And a benzylene group optionally having a butyl group or a t-butyl group). Among these, alkylene groups having 2 to 5 carbon atoms are preferable, and 1,2-ethylene group, 1,2-dimethylethylene group, 1,2-propylene group, 2-methyl-1,2-propylene group, 1,3 -Propylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 1,2-dimethyl-1,3-propylene group, 2,2-dimethyl-1,3-propylene And more preferably a 1,4-butylene group.
　ロジウム触媒の調製に使用できる溶媒は、ビスホスファイト（Ｉ）の加水分解を抑制する観点から非プロトン性溶媒が好ましく、溶媒を回収利用する観点からヒドロホルミル化反応に必要に応じて共存させる反応に不活性な溶媒と同種類の溶媒であることが好ましい。かかる溶媒としては、例えばペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、シクロヘキサンなどの飽和脂肪族炭化水素；ベンゼン、トルエン、エチルベンゼン、プロピルベンゼン、ブチルベンゼン、ｏ－キシレン、ｍ－キシレン、ｐ－キシレン、ｏ－エチルトルエン、ｍ－エチルトルエン、ｐ－エチルトルエンなどの芳香族炭化水素；イソプロパノール、イソブタノール、ネオペンチルアルコールなどのアルコール；ジエチルエーテル、ジプロピルエーテル、ブチルメチルエーテル、ｔ－ブチルメチルエーテル、ジブチルエーテル、エチルフェニルエーテル、ジフェニルエーテル、テトラヒドロフラン、１，４－ジオキサンなどのエーテル；アセトン、エチルメチルケトン、メチルプロピルケトン、ジエチルケトン、エチルプロピルケトン、ジプロピルケトンなどのケトンなどが挙げられる。これらの溶媒は１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。なかでも、少ない溶媒使用量でロジウム化合物およびビスホスファイト（Ｉ）を均一に溶解させることが可能である観点から、トルエンまたはテトラヒドロフランを使用することが好ましい。 The solvent that can be used for the preparation of the rhodium catalyst is preferably an aprotic solvent from the viewpoint of suppressing hydrolysis of bisphosphite (I), and is a reaction that coexists in the hydroformylation reaction as necessary from the viewpoint of recovering and utilizing the solvent. It is preferable that it is the same kind of solvent as an inert solvent. Examples of such solvents include saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, and cyclohexane; benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, o-xylene, m-xylene, and p-xylene. Aromatic hydrocarbons such as o-ethyltoluene, m-ethyltoluene, p-ethyltoluene; alcohols such as isopropanol, isobutanol and neopentyl alcohol; diethyl ether, dipropyl ether, butyl methyl ether, t-butyl methyl ether , Ethers such as dibutyl ether, ethyl phenyl ether, diphenyl ether, tetrahydrofuran, 1,4-dioxane; acetone, ethyl methyl ketone, methyl propyl ketone, diethyl ketone, ethyl Piruketon, etc. ketones such as dipropyl ketone. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Especially, it is preferable to use toluene or tetrahydrofuran from a viewpoint that a rhodium compound and bisphosphite (I) can be uniformly dissolved with a small amount of solvent used.
　ロジウム触媒の溶液に含まれるロジウム原子の濃度を可能な限り高めることが使用する溶媒量を低減する点で好ましく、また、ロジウム原子１モルに対するビスホスファイトの使用量を厳密に制御することが好ましいことから、ロジウム触媒の溶液は完全混合槽型反応器を用いて回分式もしくは半回分式で調製することが好ましい。
　具体的には、別途調製したロジウム化合物溶液およびビスホスファイト（Ｉ）の溶液をそれぞれ反応器に導入する方法、いずれか一方の溶液を反応器に内在させ他方を固体として導入する方法、いずれか一方を固体として反応器に内在させ他方を溶液として導入する方法、両者を固体として反応器に内在させて溶媒を導入する方法、溶媒を反応器に内在させて両者を固体として導入する方法などが挙げられる。 It is preferable to increase the concentration of rhodium atoms contained in the rhodium catalyst solution as much as possible in terms of reducing the amount of solvent used, and it is preferable to strictly control the amount of bisphosphite used per mole of rhodium atoms. Therefore, the rhodium catalyst solution is preferably prepared batch-wise or semi-batch-wise using a complete mixing tank reactor.
Specifically, either a method of introducing a separately prepared rhodium compound solution and a solution of bisphosphite (I) into the reactor, or a method of introducing one of the solutions into the reactor and introducing the other as a solid, A method of introducing one as a solid into the reactor and introducing the other as a solution, a method of introducing both into the reactor as a solid, a method of introducing a solvent, a method of introducing a solvent into the reactor and introducing both as a solid, etc. Can be mentioned.
　ロジウム触媒の溶液の調製は、窒素、アルゴン、ヘリウムなどの不活性ガス雰囲気下で行うことが好ましく、工業入手性および価格の点で窒素を用いることが好ましい。不活性ガスの圧力に特に制限はないが、通常、常圧～０．５ＭＰａ（ゲージ圧）が好ましい。 The rhodium catalyst solution is preferably prepared in an inert gas atmosphere such as nitrogen, argon, or helium, and nitrogen is preferably used in terms of industrial availability and cost. The pressure of the inert gas is not particularly limited, but usually normal pressure to 0.5 MPa (gauge pressure) is preferable.
　ロジウム触媒の溶液の調製において、ビスホスファイト（Ｉ）の使用量はロジウム原子に対して１～１００モル倍であることが好ましく、２～２０モル倍であることがより好ましい。この範囲であると、触媒活性およびジアルデヒド選択率が共に向上し、本発明の効果がより一層奏される。 In the preparation of the rhodium catalyst solution, the amount of bisphosphite (I) used is preferably 1 to 100 moles, more preferably 2 to 20 moles, relative to the rhodium atom. Within this range, both catalytic activity and dialdehyde selectivity are improved, and the effects of the present invention are further exhibited.
　本発明の製造方法で使用するロジウム触媒を調製する際の温度は１０～８０℃が好ましく、２０～５０℃がより好ましい。 The temperature at which the rhodium catalyst used in the production method of the present invention is prepared is preferably 10 to 80 ° C, more preferably 20 to 50 ° C.
　不活性ガス雰囲気下で調製したロジウム触媒の溶液は、ヒドロホルミル化反応系に供給するに先立ち、予め一酸化炭素および水素からなる混合ガス雰囲気下とすることが好ましい。一酸化炭素および水素からなる混合ガスの圧力に特に制限はないが、通常、常圧～０．５ＭＰａ（ゲージ圧）であることが好ましい。 The rhodium catalyst solution prepared in an inert gas atmosphere is preferably preliminarily placed in a mixed gas atmosphere composed of carbon monoxide and hydrogen before being supplied to the hydroformylation reaction system. The pressure of the mixed gas composed of carbon monoxide and hydrogen is not particularly limited, but it is usually preferably from normal pressure to 0.5 MPa (gauge pressure).
　本発明の製造方法は、一酸化炭素および水素からなる混合ガスの存在下、直鎖不飽和アルデヒドにロジウム触媒を好適には溶液として導入することで実施できる。 The production method of the present invention can be carried out by introducing a rhodium catalyst as a solution into a linear unsaturated aldehyde in the presence of a mixed gas composed of carbon monoxide and hydrogen.
　本発明の製造方法は、完全混合槽型反応器を用いて回分式または半回分式で実施することができるうえ、完全混合槽型反応器または管型反応器、さらにはこれらを２～３基直列に接続したものを用いて流通連続式で実施してもよい。 The production method of the present invention can be carried out batch-wise or semi-batch-wise using a complete mixing tank reactor, and is also a complete mixing tank reactor or tube reactor, and further comprises 2 to 3 of these. You may implement by a continuous flow type using what was connected in series.
　本発明の製造方法は、ロジウム触媒が溶解した直鎖不飽和アルデヒドへの、一酸化炭素および水素からなる混合ガスの溶解速度を高めることが、本発明の効果、すなわち触媒活性の向上およびジアルデヒド選択率の向上を両立させる観点から好ましい。完全混合槽型反応器または管型反応器を用いる場合には、前記混合ガスの溶解速度を高める観点から、反応器底部から混合ガスを連続的に供給してもよいし、混合室を有するエゼクタを備えた管型反応器としてのループ・ベンチュリ反応器を用いてもよい。 In the production method of the present invention, the effect of the present invention, that is, the catalytic activity is improved and the dialdehyde is increased, by increasing the dissolution rate of the mixed gas composed of carbon monoxide and hydrogen in the linear unsaturated aldehyde in which the rhodium catalyst is dissolved. It is preferable from the viewpoint of achieving both improvement in selectivity. In the case of using a complete mixing tank reactor or a tubular reactor, from the viewpoint of increasing the dissolution rate of the mixed gas, the mixed gas may be continuously supplied from the bottom of the reactor, or an ejector having a mixing chamber. A loop venturi reactor may be used as a tubular reactor equipped with
　直鎖不飽和アルデヒドとしては、例えば５－ヘキセン－１－アール、６－ヘプテン－１－アール、７－オクテン－１－アール、８－ノネン－１－アール、９－デセン－１－アール、１０－ウンデセン－１－アール、１１－ドデセン－１－アールなどが挙げられる。なかでも７－オクテン－１－アールを用いる場合に発明の効果が著しい。 Examples of linear unsaturated aldehydes include 5-hexen-1-al, 6-hepten-1-al, 7-octen-1-al, 8-nonen-1-al, 9-decene-1-al, 10 -Undecen-1-al, 11-dodesen-1-al and the like. In particular, the effect of the invention is remarkable when 7-octen-1-al is used.
　なお、本発明の製造方法においては、純度が９５質量％以上である７－オクテン－１－アールを使用することもできる。７－オクテン－１－アールは例えば２，７－オクタジエン－１－オールを銅系触媒の存在下で異性化することで製造できる。このようにして製造される７－オクテン－１－アールには１－オクタナール、７－オクテン－１－オール、ｔｒａｎｓ－６－オクテン－１－アール、ｃｉｓ－６－オクテン－１－アールなどが副生成物として含まれる。これらの副生成物は本発明の製造方法で用いるロジウム触媒を著しく被毒するものではないことから、これら不純物を含有するままで７－オクテン－１－アールをヒドロホルミル化反応することが可能である。すなわち、直鎖不飽和アルデヒドの純度によって発明の範囲が制限されるものではない。 In the production method of the present invention, 7-octen-1-al having a purity of 95% by mass or more can also be used. 7-octen-1-al can be produced, for example, by isomerizing 2,7-octadien-1-ol in the presence of a copper-based catalyst. The 7-octen-1-al produced in this way includes 1-octanal, 7-octen-1-ol, trans-6-octen-1-al, cis-6-octen-1-al and the like. Included as product. Since these by-products do not significantly poison the rhodium catalyst used in the production method of the present invention, it is possible to hydroformylate 7-octen-1-al while containing these impurities. . That is, the scope of the invention is not limited by the purity of the linear unsaturated aldehyde.
　本発明の製造方法においては、反応開始時の反応液中の含水量が０．１～５００ミリモル／ｋｇでありかつ反応液中のカルボン酸の含有量がカルボキシル基として０．１～５０ミリモル／ｋｇである状態で反応を行っても、良好に反応が進行する。反応開始時の反応液中の含水量は０．１～５０ミリモル／ｋｇであることが好ましい。また反応液中のカルボン酸の含有量はカルボキシル基として０．１～２５ミリモル／ｋｇであることが好ましい。かかる条件を満足する範囲で、本発明の製造方法において原料として用いる直鎖不飽和アルデヒドは、水および／またはカルボン酸を含有していても良い。 In the production method of the present invention, the water content in the reaction solution at the start of the reaction is 0.1 to 500 mmol / kg, and the carboxylic acid content in the reaction solution is 0.1 to 50 mmol / kg as carboxyl groups. Even if the reaction is carried out in kg, the reaction proceeds well. The water content in the reaction solution at the start of the reaction is preferably 0.1 to 50 mmol / kg. The content of carboxylic acid in the reaction solution is preferably 0.1 to 25 mmol / kg as carboxyl groups. As long as these conditions are satisfied, the linear unsaturated aldehyde used as a raw material in the production method of the present invention may contain water and / or carboxylic acid.
　本発明の製造方法は溶媒の存在下で行ってもよい。溶媒としては、ロジウム触媒の溶液を調製する際に使用することができる、前記した溶媒と同じものが好ましく挙げられる。溶媒を存在させる場合、その使用量は反応液全体に対して０．１～２０質量％が好ましく、１～１０質量％がより好ましい。なお、溶媒の使用量とは、ロジウム触媒の溶液として供給される溶媒および別途反応系に供給される溶媒の合計を意味する。 The production method of the present invention may be performed in the presence of a solvent. Preferred examples of the solvent include the same solvents as those described above that can be used when preparing a rhodium catalyst solution. When a solvent is present, the amount used is preferably from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, based on the entire reaction solution. In addition, the usage-amount of a solvent means the sum total of the solvent supplied as a solution of a rhodium catalyst, and the solvent supplied separately to a reaction system.
　本発明の製造方法においては、反応液中のロジウム使用量は、ロジウム原子として１．０×１０－４～６．０×１０－１ミリモル／ｋｇであることが好ましく、１．０×１０－３～２．５×１０－１ミリモル／ｋｇであることがより好ましく、１．０×１０－３～２．５×１０－２ミリモル／ｋｇであることがさらに好ましい。反応液中のビスホスファイト（Ｉ）の使用量はロジウム原子に対して１～１００モル倍であることが好ましく、２～２０モル倍であることがより好ましい。これらの範囲において、高い触媒活性および高いジアルデヒド選択率を達成できる。 In the production method of the present invention, the amount of rhodium used in the reaction solution is preferably 1.0 × 10 −4 to 6.0 × 10 −1 mmol / kg as rhodium atoms, and 1.0 × 10 − It is more preferably 3 to 2.5 × 10 −1 mmol / kg, and further preferably 1.0 × 10 −3 to 2.5 × 10 −2 mmol / kg. The amount of bisphosphite (I) used in the reaction solution is preferably 1 to 100 mol times, more preferably 2 to 20 mol times relative to the rhodium atom. In these ranges, high catalytic activity and high dialdehyde selectivity can be achieved.
　本発明の製造方法において、反応温度は５０～１３０℃が好ましく、１００～１２０℃が好ましい。反応温度が前記の範囲であるとロジウム触媒が分解することなく、高い触媒活性および高いジアルデヒド選択率を達成できる。 In the production method of the present invention, the reaction temperature is preferably 50 to 130 ° C, more preferably 100 to 120 ° C. When the reaction temperature is within the above range, high catalyst activity and high dialdehyde selectivity can be achieved without decomposition of the rhodium catalyst.
　本発明の製造方法において、反応に用いる一酸化炭素および水素からなる混合ガスの組成比は、モル比として、通常、一酸化炭素／水素＝０．１／１～１０／１の範囲であり、０．５／１～５／１の範囲が好ましく、１／１～３／１がより好ましい。かかる混合ガスの反応時の圧力は０．５～１０．０ＭＰａ（ゲージ圧）であることが好ましく、１．０～５．０ＭＰａ（ゲージ圧）であることがより好ましい。 In the production method of the present invention, the composition ratio of the mixed gas composed of carbon monoxide and hydrogen used for the reaction is usually in the range of carbon monoxide / hydrogen = 0.1 / 1 to 10/1 as a molar ratio. The range of 0.5 / 1 to 5/1 is preferable, and 1/1 to 3/1 is more preferable. The pressure during the reaction of such a mixed gas is preferably 0.5 to 10.0 MPa (gauge pressure), more preferably 1.0 to 5.0 MPa (gauge pressure).
　本発明の製造方法の特徴は、反応開始時の一酸化炭素および水素からなる混合ガス圧力を相対的に高い値に設定して直鎖不飽和アルデヒドのヒドロホルミル化反応を行い、反応の進行に伴って、一酸化炭素および水素からなる混合ガスの反応圧力を低下させることにある。より好適には、本発明の製造方法においては、直鎖不飽和アルデヒドの転化率が７０％を超えた段階において、一酸化炭素および水素からなる混合ガスの反応圧力を段階的または連続的に反応開始時の圧力の３０～８０％、好ましくは４０～７０％の圧力になるように制御して反応を行う。
　本発明の製造方法の実施態様としては、例えば回分式もしくは半回分式反応器を用いる場合は、直鎖不飽和アルデヒドの転化率が７０％を超えた段階において、一酸化炭素および水素からなる混合ガスの反応圧力を段階的または連続的に反応開始時の圧力の３０～８０％、好ましくは４０～７０％の圧力になるように制御して反応をさらに行う。あるいは、回分式反応器を複数連結し、第１反応器において直鎖不飽和アルデヒドの転化率が７０％を超えるまで反応を行い、次いで第１反応器中の反応液を、一酸化炭素および水素からなる混合ガスの反応圧力が第１反応器の３０～８０％である第２反応器に移送し、引続き反応を行う工程を有する、流通連続式の反応形式にて実施してもよい。このように反応圧力を反応の進行に伴って制御することにより、得られるジアルデヒド収率低下がなく、ロジウム使用量を削減でき、ジアルデヒドの製造原価に占める触媒費用を削減することができる。 A feature of the production method of the present invention is that a hydroformylation reaction of a linear unsaturated aldehyde is carried out by setting a mixed gas pressure composed of carbon monoxide and hydrogen at the start of the reaction to a relatively high value. Thus, the reaction pressure of the mixed gas composed of carbon monoxide and hydrogen is reduced. More preferably, in the production method of the present invention, when the conversion rate of the linear unsaturated aldehyde exceeds 70%, the reaction pressure of the mixed gas composed of carbon monoxide and hydrogen is reacted stepwise or continuously. The reaction is carried out while controlling the pressure to be 30 to 80%, preferably 40 to 70% of the starting pressure.
As an embodiment of the production method of the present invention, for example, when a batch-type or semi-batch-type reactor is used, in the stage where the conversion rate of the linear unsaturated aldehyde exceeds 70%, mixing of carbon monoxide and hydrogen is performed. The reaction is further carried out by controlling the reaction pressure of the gas stepwise or continuously so that it is 30 to 80%, preferably 40 to 70% of the pressure at the start of the reaction. Alternatively, a plurality of batch reactors are connected, and the reaction is performed in the first reactor until the conversion rate of the linear unsaturated aldehyde exceeds 70%, and then the reaction solution in the first reactor is mixed with carbon monoxide and hydrogen. The reaction may be carried out in a continuous flow type reaction system having a step of transferring to a second reactor where the reaction pressure of the mixed gas is 30 to 80% of that of the first reactor and continuing the reaction. Thus, by controlling the reaction pressure as the reaction proceeds, the yield of the dialdehyde obtained is not reduced, the amount of rhodium used can be reduced, and the catalyst cost in the production cost of the dialdehyde can be reduced.
　なお、本発明の製造方法においては、必要に応じてビスホスファイト（Ｉ）以外のリン化合物をさらに共存させても良い。かかるリン化合物としては、例えばトリイソプロピルホスフィン、トリ－ｎ－ブチルホスフィン、トリ－ｔ－ブチルホスフィン、トリベンジルホスフィン、トリフェニルホスフィン、トリス（ｐ－メトキシフェニル）ホスフィン、トリス（ｐ－Ｎ，Ｎ－ジメチルアミノフェニル）ホスフィン、トリス（ｐ－フルオロフェニル）ホスフィン、トリ－ｏ－トリルホスフィン、トリ－ｍ－トリルホスフィン、トリ－ｐ－トリルホスフィン、トリス（ペンタフルオロフェニル）ホスフィン、ビス（ペンタフルオロフェニル）フェニルホスフィン、ジフェニル（ペンタフルオロフェニル）ホスフィン、メチルジフェニルホスフィン、エチルジフェニルホスフィン、シクロヘキシルジフェニルホスフィン、ジメチルフェニルホスフィン、ジエチルフェニルホスフィン、２－フリルジフェニルホスフィン、２－ピリジルジフェニルホスフィン、４－ピリジルジフェニルホスフィン、ｍ－ジフェニルホスフィノベンゼンスルホン酸またはその金属塩、ｐ－ジフェニルホスフィノ安息香酸またはその金属塩、ｐ－ジフェニルホスフィノフェニルホスホン酸またはその金属塩などのホスフィン；トリエチルホスファイト、トリフェニルホスファイト、トリス（ｐ－メトキシフェニル）ホスファイト、トリス（ｏ－メチルフェニル）ホスファイト、トリス（ｍ－メチルフェニル）ホスファイト、トリス（ｐ－メチルフェニル）ホスファイト、トリス（ｏ－エチルフェニル）ホスファイト、トリス（ｍ－エチルフェニル）ホスファイト、トリス（ｐ－エチルフェニル）ホスファイト、トリス（ｏ－プロピルフェニル）ホスファイト、トリス（ｍ－プロピルフェニル）ホスファイト、トリス（ｐ－プロピルフェニル）ホスファイト、トリス（ｏ－イソプロピルフェニル）ホスファイト、トリス（ｍ－イソプロピルフェニル）ホスファイト、トリス（ｐ－イソプロピルフェニル）ホスファイト、トリス（ｏ－ｔ－ブチルフェニル）ホスファイト、トリス（ｐ－ｔ－ブチルフェニル）ホスファイト、トリス（ｐ－トリフルオロメチルフェニル）ホスファイト、トリス（２，４－ジメチルフェニル）ホスファイト、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト、トリス（２－ｔ－ブチル－４－メチルフェニル）ホスファイトなどのホスファイトなどが挙げられる。リン化合物をさらに共存させる場合、その使用量はロジウム原子に対して１～１００モル倍であることが好ましく、２～２０モル倍であることがより好ましい。 In addition, in the manufacturing method of this invention, you may further coexist phosphorus compounds other than bisphosphite (I) as needed. Examples of such phosphorus compounds include triisopropylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tribenzylphosphine, triphenylphosphine, tris (p-methoxyphenyl) phosphine, tris (pN, N— Dimethylaminophenyl) phosphine, tris (p-fluorophenyl) phosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris (pentafluorophenyl) phosphine, bis (pentafluorophenyl) Phenylphosphine, diphenyl (pentafluorophenyl) phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, cyclohexyldiphenylphosphine, dimethylphenylphosphine, diethylphenyl Sphin, 2-furyldiphenylphosphine, 2-pyridyldiphenylphosphine, 4-pyridyldiphenylphosphine, m-diphenylphosphinobenzenesulfonic acid or its metal salt, p-diphenylphosphinobenzoic acid or its metal salt, p-diphenylphosphino Phosphines such as phenylphosphonic acid or metal salts thereof; triethyl phosphite, triphenyl phosphite, tris (p-methoxyphenyl) phosphite, tris (o-methylphenyl) phosphite, tris (m-methylphenyl) phosphite, Tris (p-methylphenyl) phosphite, tris (o-ethylphenyl) phosphite, tris (m-ethylphenyl) phosphite, tris (p-ethylphenyl) phosphite, tris (o-propylphenyl) Nyl) phosphite, tris (m-propylphenyl) phosphite, tris (p-propylphenyl) phosphite, tris (o-isopropylphenyl) phosphite, tris (m-isopropylphenyl) phosphite, tris (p-isopropyl) Phenyl) phosphite, Tris (ot-butylphenyl) phosphite, Tris (pt-butylphenyl) phosphite, Tris (p-trifluoromethylphenyl) phosphite, Tris (2,4-dimethylphenyl) Examples thereof include phosphites such as phosphite, tris (2,4-di-t-butylphenyl) phosphite, and tris (2-t-butyl-4-methylphenyl) phosphite. In the case where a phosphorus compound is further allowed to coexist, the amount used is preferably 1 to 100 mol times, more preferably 2 to 20 mol times relative to the rhodium atom.
　本発明の製造方法においては、必要に応じて含窒素化合物をさらに共存させても良い。かかる含窒素化合物としては、例えばトリエチルアミン、トリブチルアミン、トリ－ｎ－オクチルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチル－１，２－ジアミノエタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチル－１，３－ジアミノプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチル－１，４－ジアミノブタン、Ｎ，Ｎ－ジエチルエタノールアミン、トリエタノールアミン、Ｎ－メチルピペリジン、Ｎ－メチルピロリジン、Ｎ－メチルモルホリン、ピリジン、ピコリン、ルチジン、コリジン、キノリンなどが挙げられる。含窒素化合物をさらに共存させる場合、その使用量はロジウム原子に対して１００～３０００モル倍であるのが好ましく、５００～２０００モル倍であることがより好ましい。含窒素化合物をさらに共存させると、目的生成物であるジアルデヒドが反応条件下においてさらに反応して高沸物となってしまうことを抑制できる。 In the production method of the present invention, a nitrogen-containing compound may further coexist as necessary. Examples of such nitrogen-containing compounds include triethylamine, tributylamine, tri-n-octylamine, N, N, N ′, N′-tetramethyl-1,2-diaminoethane, N, N, N ′, N′-. Tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,4-diaminobutane, N, N-diethylethanolamine, triethanolamine, N-methylpiperidine, N-methyl Examples include pyrrolidine, N-methylmorpholine, pyridine, picoline, lutidine, collidine, and quinoline. When the nitrogen-containing compound is further allowed to coexist, the amount used is preferably 100 to 3000 mol times, more preferably 500 to 2000 mol times with respect to the rhodium atom. When a nitrogen-containing compound is further allowed to coexist, it can be suppressed that the target product dialdehyde further reacts under reaction conditions to become a high boiling point product.
　本発明の製造方法においては、ヒドロホルミル化反応終了後の反応液に含まれるロジウムの含有量は工業的に許容できる程度に少ないため、反応液からロジウムを回収する操作を行わずに反応液をそのまま水素化反応や還元アミノ化反応などの次の反応に直接用いることができる。もちろん、所望に応じ、反応液からジアルデヒドをロジウム触媒成分と分離して精製する工程を行っても良い。かかる反応液からのジアルデヒドの分離・精製方法に特に制限はなく、公知の方法を適用できる。例えば、ヒドロホルミル化反応液から低沸点成分を減圧下に留去し、残留物をさらに蒸留精製して未反応原料、ジアルデヒドおよびロジウム触媒を含む蒸留残渣に分離できる。未反応原料および蒸留残渣は、本発明の製造方法に再使用してもよい。また、蒸留分離に先立ち、残留物を蒸発、抽出、吸着などの方法を施してロジウム触媒を構成する成分を分離してもよい。 In the production method of the present invention, since the rhodium content in the reaction solution after completion of the hydroformylation reaction is industrially acceptable, the reaction solution is left as it is without performing the operation of recovering rhodium from the reaction solution. It can be used directly in the next reaction such as a hydrogenation reaction or a reductive amination reaction. Of course, if desired, a step of purifying the dialdehyde from the reaction solution by separating it from the rhodium catalyst component may be performed. There is no particular limitation on the method for separating and purifying dialdehyde from the reaction solution, and a known method can be applied. For example, low-boiling components can be distilled off from the hydroformylation reaction solution under reduced pressure, and the residue can be further purified by distillation to separate it into a distillation residue containing unreacted raw materials, dialdehyde and rhodium catalyst. You may reuse an unreacted raw material and distillation residue for the manufacturing method of this invention. Prior to distillation separation, the constituents of the rhodium catalyst may be separated by subjecting the residue to methods such as evaporation, extraction, and adsorption.
　以下、実施例および比較例により本発明をさらに詳細に説明するが、本発明はかかる実施例および比較例により何ら限定されるものではない。
　各実施例および参考例において原料として用いた７－オクテン－１－アールは純度９５．４質量％であり、主な不純物は１－オクタナール、ｔｒａｎｓ－６－オクテン－１－アール、ｃｉｓ－６－オクテン－１－アールである。ロジウム触媒の調製は、特に断りのない限り、室温、常圧、窒素雰囲気下で行い、原料および溶媒は予め蒸留精製後、窒素置換したものを用いた。
ビスホスファイトとしては、下記の化学式 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by this Example and comparative example.
The 7-octen-1-al used as a raw material in each example and reference example has a purity of 95.4% by mass, and the main impurities are 1-octanal, trans-6-octen-1-al, cis-6- Octen-1-al. Unless otherwise specified, the rhodium catalyst was prepared at room temperature, normal pressure, and nitrogen atmosphere, and the raw materials and solvent were previously purified by distillation and purged with nitrogen.
Bisphosphite has the following chemical formula
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
に示される化合物を用いた。これらは、公知の方法に従って合成した。
　反応液中の７－オクテン－１－アールの消費量（転化率）、目的生成物である１，９－ノナンジアール、２－メチル－１，８－オクタンジアールおよび他の生成物の生成量はガスクロマトグラフィーにより分析し、定量した。 The compound shown in was used. These were synthesized according to known methods.
The amount of 7-octen-1-al consumed in the reaction solution (conversion rate), the amount of 1,9-nonanedial, 2-methyl-1,8-octanedial, and other products as the target products are Analysis and quantification by gas chromatography.
実施例１
　磁気回転子を備えた内容積１００ｍＬの三口フラスコに窒素雰囲気下、Ｒｈ（ａｃａｃ）（ＣＯ）２を２９．２ｍｇ（０．１１３ミリモル）、ビスホスファイトＡを７４４．７ｍｇ（０．７５９ミリモル）、トルエン７７．３８ｇを入れ、５０℃で３０分間攪拌して溶解させた後、室温に冷却し、一酸化炭素／水素＝１／１（モル比）の混合ガス雰囲気に置換してからさらに３０分間攪拌してロジウム触媒の溶液を調製した。
　一方、マックスブレンド翼、ロジウム触媒溶液導入口、ガス導入口、ガス排気口、およびサンプリング口を備えた内容積３Ｌのオートクレーブの内部を一酸化炭素／水素＝１／１（モル比）の混合ガス雰囲気に置換してから、７－オクテン－１－アール（純度９５．４質量％）７１７．００ｇ、水５．７０ｇ（３１６．４１ミリモル）およびオクタン酸２．２０ｇ（１５．２６ミリモル）を仕込んだ。オートクレーブ内部を一酸化炭素／水素＝１／１（モル比）の混合ガスで２．０ＭＰａ（ゲージ圧）に加圧し、５００ｒｐｍで十分に攪拌しながら１１０℃まで昇温した。次いで、先に調製したロジウム触媒溶液５．７６ｇ（ロジウム原子を０．００８４ミリモル、ビスホスファイトＡを０．０５５９ミリモル含む）を一酸化炭素／水素＝１／１（モル比）の混合ガスでオートクレーブ内部に圧送した後、攪拌しながら５分以内に内温を１２０℃に昇温し、かつ一酸化炭素／水素＝１／１（モル比）の混合ガスを用いてオートクレーブ内部の全圧を５．０ＭＰａ（ゲージ圧）にし、反応を開始した。反応開始時の反応液中のロジウム濃度はロジウム原子として０．０１１５ミリモル／ｋｇであり、ビスホスファイト使用量はロジウム原子に対して６．７２モル倍であり、含水量は４３０ミリモル／ｋｇであり、カルボン酸含有量はカルボキシル基として２０．８８ミリモル／ｋｇであった。
　反応液の内温が１２０℃に到達した時間を反応開始時間０時間とした際の、反応８時間後の７－オクテン－１－アールの転化率は８５．２％であり、ジアルデヒド選択率は９２．２％（１，９－ノナンジアール／２－メチル－１，８－オクタンジアール＝８４．６／１５．４；以下、単に直鎖／分岐比と称する）であり、異性体など（６－オクテン－１－アール、オクタナールなど）の選択率は７．８％であった。その後、３０秒以内にオートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を２．０ＭＰａ（ゲージ圧）に減じ、さらに４時間反応した（反応時間の合計は１２時間である）。反応終了時の７－オクテン－１－アールの転化率は９７．３％であり、ジアルデヒド選択率は９１．９％（直鎖／分岐比＝８５．０／１５．０）であり（ジアルデヒド収率：８９．４％）、異性体などの選択率は８．１％であった。 Example 1
In a 100 mL three-necked flask equipped with a magnetic rotor, 29.2 mg (0.113 mmol) of Rh (acac) (CO) 2 and 744.7 mg (0.759 mmol) of bisphosphite A were added under a nitrogen atmosphere. Then, 77.38 g of toluene was added, dissolved by stirring at 50 ° C. for 30 minutes, cooled to room temperature, and replaced with a mixed gas atmosphere of carbon monoxide / hydrogen = 1/1 (molar ratio). A solution of rhodium catalyst was prepared by stirring for a minute.
On the other hand, a mixed gas of carbon monoxide / hydrogen = 1/1 (molar ratio) inside an autoclave having an internal volume of 3 L equipped with a Max blend blade, a rhodium catalyst solution inlet, a gas inlet, a gas outlet, and a sampling port After substituting for the atmosphere, 717.00 g of 7-octen-1-al (purity 95.4% by mass), 5.70 g (316.41 mmol) of water and 2.20 g (15.26 mmol) of octanoic acid were charged. It is. The inside of the autoclave was pressurized to 2.0 MPa (gauge pressure) with a mixed gas of carbon monoxide / hydrogen = 1/1 (molar ratio), and the temperature was raised to 110 ° C. with sufficient stirring at 500 rpm. Next, 5.76 g of the rhodium catalyst solution prepared previously (containing 0.0084 mmol of rhodium atoms and 0.0559 mmol of bisphosphite A) in a mixed gas of carbon monoxide / hydrogen = 1/1 (molar ratio). After pumping into the autoclave, the internal temperature is raised to 120 ° C. within 5 minutes with stirring, and the total pressure inside the autoclave is adjusted using a mixed gas of carbon monoxide / hydrogen = 1/1 (molar ratio). The reaction was started at 5.0 MPa (gauge pressure). The rhodium concentration in the reaction solution at the start of the reaction was 0.0115 mmol / kg as rhodium atoms, the amount of bisphosphite used was 6.72 mol times the rhodium atoms, and the water content was 430 mmol / kg. The carboxylic acid content was 20.88 mmol / kg as a carboxyl group.
The conversion rate of 7-octen-1-al after 8 hours of reaction was 85.2% when the time when the internal temperature of the reaction solution reached 120 ° C. was defined as 0 hour of reaction start, and dialdehyde selectivity Is 92.2% (1,9-nonanediar / 2-methyl-1,8-octanediar = 84.6 / 15.4; hereinafter simply referred to as linear / branch ratio), The selectivity for 6-octen-1-al, octanal, etc.) was 7.8%. Thereafter, the mixed gas pressure of carbon monoxide / hydrogen inside the autoclave = 1/1 (molar ratio) was reduced to 2.0 MPa (gauge pressure) within 30 seconds, and the reaction was further continued for 4 hours (the total reaction time was 12 hours). Is). At the end of the reaction, the conversion of 7-octen-1-al was 97.3% and the dialdehyde selectivity was 91.9% (linear / branch ratio = 85.0 / 15.0) Aldehyde yield: 89.4%), and selectivity for isomers and the like was 8.1%.
実施例２
　実施例１において、水およびオクタン酸を仕込まなかった以外は、実施例１と同様に反応を実施した。反応開始時の反応液中のロジウム濃度はロジウム原子として０．０１１６ミリモル／ｋｇであり、ビスホスファイト使用量はロジウム原子に対して６．７２モル倍であった。
　反応８時間後の７－オクテン－１－アールの転化率は８５．２％であり、ジアルデヒド選択率は９２．２％（直鎖／分岐比＝８４．６／１５．４）であり、異性体などの選択率は７．８％であった。その後、３０秒以内にオートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を２．０ＭＰａ（ゲージ圧）に減じ、さらに４時間反応した（反応時間の合計は１２時間である）。反応終了時の７－オクテン－１－アールの転化率は９７．３％であり、ジアルデヒド選択率は９１．９％（直鎖／分岐比＝８５．０／１５．０）であり（ジアルデヒド収率：８９．４％）、異性体などの選択率は８．１％であった。 Example 2
In Example 1, the reaction was carried out in the same manner as in Example 1 except that water and octanoic acid were not charged. The rhodium concentration in the reaction solution at the start of the reaction was 0.0116 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.72 mol times the rhodium atoms.
The conversion of 7-octen-1-al after 8 hours of the reaction was 85.2%, the dialdehyde selectivity was 92.2% (linear / branch ratio = 84.6 / 15.4), The selectivity for isomers and the like was 7.8%. Thereafter, the mixed gas pressure of carbon monoxide / hydrogen inside the autoclave = 1/1 (molar ratio) was reduced to 2.0 MPa (gauge pressure) within 30 seconds, and the reaction was further continued for 4 hours (the total reaction time was 12 hours). Is). At the end of the reaction, the conversion of 7-octen-1-al was 97.3% and the dialdehyde selectivity was 91.9% (linear / branch ratio = 85.0 / 15.0) Aldehyde yield: 89.4%), and selectivity for isomers and the like was 8.1%.
実施例３
　実施例１において、Ｒｈ（ａｃａｃ）（ＣＯ）２を２９．２ｍｇ（０．１１３ミリモル）の代わりに１５．８ｍｇ（０．０６１ミリモル）用いること、ビスホスファイトＡを７４４．７ｍｇ（０．７５９ミリモル）の代わりに４０１．７ｍｇ（０．４０９ミリモル）用いること、水およびオクタン酸を仕込まないこと、反応開始から１２時間まではオートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を５．０ＭＰａ（ゲージ圧）とし、その後、３０秒以内にオートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を２．０ＭＰａ（ゲージ圧）に減じさらに６時間反応する（反応時間の合計は１８時間である）以外は、実施例１と同様に反応を実施した。反応開始時の反応液中のロジウム濃度はロジウム原子として０．００６３ミリモル／ｋｇであり、ビスホスファイト使用量はロジウム原子に対して６．７モル倍であった。
　反応１２時間後の７－オクテン－１－アールの転化率は８４．７％であり、ジアルデヒド選択率は８９．４％（直鎖／分岐比＝８４．６／１５．４）であり、異性体などの選択率は１０．６％であった。その後、オートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を２．０ＭＰａ（ゲージ圧）に減じ更に６時間反応した後の７－オクテン－１－アールの転化率は９６．７％であり、ジアルデヒド選択率は８９．２％（直鎖／分岐比＝８４．９／１５．１）であり（ジアルデヒド収率：８６．３％）、異性体などの選択率は１０．２％であった。 Example 3
In Example 1, 15.8 mg (0.061 mmol) was used instead of 29.2 mg (0.113 mmol) of Rh (acac) (CO) 2 and 744.7 mg (0.759 mmol) of bisphosphite A was used. 401.7 mg (0.409 mmol) is used instead of mmol), water and octanoic acid are not charged, and carbon monoxide / hydrogen inside the autoclave is 1/1 (molar ratio) up to 12 hours from the start of the reaction. The mixed gas pressure is set to 5.0 MPa (gauge pressure), and then the mixed gas pressure of carbon monoxide / hydrogen = 1/1 (molar ratio) inside the autoclave is reduced to 2.0 MPa (gauge pressure) within 30 seconds. The reaction was carried out in the same manner as in Example 1 except that the reaction was performed for 6 hours (the total reaction time was 18 hours). The rhodium concentration in the reaction solution at the start of the reaction was 0.0063 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.7 mol times the rhodium atoms.
The conversion of 7-octen-1-al after 12 hours of reaction was 84.7% and the dialdehyde selectivity was 89.4% (linear / branch ratio = 84.6 / 15.4), The selectivity for isomers and the like was 10.6%. Thereafter, the conversion rate of 7-octen-1-al after reducing the mixed gas pressure of carbon monoxide / hydrogen = 1/1 (molar ratio) inside the autoclave to 2.0 MPa (gauge pressure) and further reacting for 6 hours is 96.7%, dialdehyde selectivity is 89.2% (linear / branch ratio = 84.9 / 15.1) (dialdehyde yield: 86.3%), selection of isomers, etc. The rate was 10.2%.
実施例４
　実施例１において、Ｒｈ（ａｃａｃ）（ＣＯ）２を２９．２ｍｇ（０．１１３ミリモル）の代わりに３３．６ｍｇ（０．１３０ミリモル）を用いること、ビスホスファイトＡ７４４．７ｍｇ（０．７５９ミリモル）の代わりにビスホスファイトＢを８５６．４ｍｇ（０．８７３ミリモル）を用いること、水およびオクタン酸を仕込まないこと、反応開始から８時間まではオートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を５．０ＭＰａ（ゲージ圧）とし、その後、３０秒以内にオートクレーブ内部の水素／一酸化炭素＝１／１（モル比）の混合ガス圧力を２．０ＭＰａ（ゲージ圧）に減じさらに４時間反応する（反応時間の合計は１２時間である）以外は、実施例１と同様に反応を実施した。反応開始時の反応液中のロジウム濃度はロジウム原子として０．０１３４ミリモル／ｋｇであり、ビスホスファイト使用量はロジウム原子に対して６．７モル倍であった。
　反応８時間後の７－オクテン－１－アールの転化率は８３．８％であり、ジアルデヒド選択率は９２．２％（直鎖／分岐比＝７９．６／２０．４）であり、異性体などの選択率は７．８％であった。その後、オートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を２．０ＭＰａ（ゲージ圧）に減じ更に４時間反応した後の７－オクテン－１－アールの転化率は９６．８％であり、ジアルデヒド選択率は９２．０％（直鎖／分岐比＝８０．１／１９．９）であり（ジアルデヒド収率：８９．１％）、異性体などの選択率は８．０％であった。 Example 4
In Example 1, 33.6 mg (0.130 mmol) was used instead of 29.2 mg (0.113 mmol) of Rh (acac) (CO) 2, and 474.7 mg (0.759 mmol) of bisphosphite A ) Instead of 856.4 mg (0.873 mmol) of bisphosphite B, no charge of water and octanoic acid, and carbon monoxide / hydrogen inside the autoclave for 1/1 hours from the start of the reaction = 1/1 The mixed gas pressure of (molar ratio) was set to 5.0 MPa (gauge pressure), and then the mixed gas pressure of hydrogen / carbon monoxide = 1/1 (molar ratio) inside the autoclave was set to 2.0 MPa (gauge) within 30 seconds. The reaction was carried out in the same manner as in Example 1 except that the reaction was continued for 4 hours (the total reaction time was 12 hours). The rhodium concentration in the reaction solution at the start of the reaction was 0.0134 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.7 mol times the rhodium atoms.
The conversion of 7-octen-1-al after 8 hours of the reaction was 83.8%, and the dialdehyde selectivity was 92.2% (linear / branch ratio = 79.6 / 20.4). The selectivity for isomers and the like was 7.8%. Thereafter, the conversion rate of 7-octen-1-al after reducing the mixed gas pressure of carbon monoxide / hydrogen = 1/1 (molar ratio) inside the autoclave to 2.0 MPa (gauge pressure) and further reacting for 4 hours is 96.8%, dialdehyde selectivity is 92.0% (linear / branch ratio = 80.1 / 19.9) (dialdehyde yield: 89.1%), selection of isomers, etc. The rate was 8.0%.
実施例５
　実施例１において、Ｒｈ（ａｃａｃ）（ＣＯ）２を２９．２ｍｇ（０．１１３ミリモル）の代わりに４７．３ｍｇ（０．１８３ミリモル）を用いること、ビスホスファイトＡを７４４．７ｍｇ（０．７５９ミリモル）の代わりにビスホスファイトＣを１２０６．４ｍｇ（１．２２９ミリモル）を用いること、水およびオクタン酸を仕込まないこと、反応開始から８時間まではオートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を５．０ＭＰａ（ゲージ圧）とし、その後、３０秒以内にオートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を２．０ＭＰａ（ゲージ圧）に減じさらに４時間反応する（反応時間の合計は１２時間である）以外は、実施例１と同様に反応を実施した。反応開始時の反応液中のロジウム濃度はロジウム原子として０．０１８９ミリモル／ｋｇであり、ビスホスファイト使用量はロジウム原子に対して６．７２モル倍であった。
　反応８時間後の７－オクテン－１－アールの転化率は８３．４％であり、ジアルデヒド選択率が９２．７％（直鎖／分岐比＝７９．６／２０．４）であり、異性体などの選択率は７．８％であった。その後、オートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を２．０ＭＰａ（ゲージ圧）に減じ更に４時間反応した後の７－オクテン－１－アールの転化率は９６．９％であり、ジアルデヒド選択率が９２．４％（直鎖／分岐比＝８０．０／２０．０）であり（ジアルデヒド収率：８９．５％）、異性体などの選択率は７．６％であった。 Example 5
In Example 1, 47.3 mg (0.183 mmol) was used instead of 29.2 mg (0.113 mmol) of Rh (acac) (CO) 2, and 744.7 mg (0. 0.1 mmol) of bisphosphite A was used. In place of 759 mmol), 1206.4 mg (1.229 mmol) of bisphosphite C, no charge of water and octanoic acid, and carbon monoxide / hydrogen inside the autoclave = 1 for 8 hours from the start of the reaction / 1 (molar ratio) mixed gas pressure is set to 5.0 MPa (gauge pressure), and then within 30 seconds, the mixed gas pressure of carbon monoxide / hydrogen inside the autoclave = 1/1 (molar ratio) is 2.0 MPa. The reaction was carried out in the same manner as in Example 1 except that the pressure was reduced to (gauge pressure) and further reacted for 4 hours (total reaction time was 12 hours). The rhodium concentration in the reaction solution at the start of the reaction was 0.0189 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.72 mol times the rhodium atoms.
The conversion of 7-octen-1-al after 8 hours of the reaction was 83.4%, the dialdehyde selectivity was 92.7% (linear / branch ratio = 79.6 / 20.4), The selectivity for isomers and the like was 7.8%. Thereafter, the conversion rate of 7-octen-1-al after reducing the mixed gas pressure of carbon monoxide / hydrogen = 1/1 (molar ratio) inside the autoclave to 2.0 MPa (gauge pressure) and further reacting for 4 hours is 96.9%, dialdehyde selectivity is 92.4% (linear / branch ratio = 80.0 / 20.0) (dialdehyde yield: 89.5%), selection of isomers, etc. The rate was 7.6%.
参考例１（実施例１および２との比較）
　実施例１において、Ｒｈ（ａｃａｃ）（ＣＯ）２を２９．２ｍｇ（０．１１３ミリモル）の代わりに３３．４ｍｇ（０．１３０ミリモル）を用いること、ビスホスファイトＡを７４４．７ｍｇ（０．７５９ミリモル）の代わりに８５１．７ｍｇ（０．８６８ミリモル）を用いること、水およびオクタン酸を仕込まないこと、オートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を５．０ＭＰａ（ゲージ圧）一定として１２時間反応を行った以外は、実施例１と同様に反応を実施した。反応開始時の反応液中のロジウム濃度はロジウム原子として０．０１３４ミリモル／ｋｇであり、ビスホスファイト使用量はロジウム原子に対して６．６７モル倍であった。
　反応後の７－オクテン－１－アールの転化率は９６．７％であり、ジアルデヒド選択率は９２．５％（直鎖／分岐比＝８４．６／１５．４）であり（ジアルデヒド収率：８９．４％）、異性体などの選択率は７．５％であった。 Reference Example 1 (Comparison with Examples 1 and 2)
In Example 1, 33.4 mg (0.130 mmol) was used instead of 29.2 mg (0.113 mmol) of Rh (acac) (CO) 2, and 744.7 mg (0. 30 mmol) of bisphosphite A was used. 759 mmol) is used instead of 851.7 mg (0.868 mmol), water and octanoic acid are not charged, and the mixed gas pressure of carbon monoxide / hydrogen inside the autoclave = 1/1 (molar ratio) is 5 The reaction was performed in the same manner as in Example 1 except that the reaction was performed for 12 hours at a constant 0.0 MPa (gauge pressure). The rhodium concentration in the reaction solution at the start of the reaction was 0.0134 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.67 mol times the rhodium atoms.
The 7-octen-1-al conversion after the reaction was 96.7%, and the dialdehyde selectivity was 92.5% (linear / branch ratio = 84.6 / 15.4) (dialdehyde). (Yield: 89.4%), and the selectivity for isomers and the like was 7.5%.
参考例２（実施例３との比較）
　実施例１において、Ｒｈ（ａｃａｃ）（ＣＯ）２を２９．２ｍｇ（０．１１３ミリモル）の代わりに１７．７ｍｇ（０．０６９ミリモル）を用いること、ビスホスファイトＡを７４４．７ｍｇ（０．７５９ミリモル）の代わりに４５１．０ｍｇ（０．４６０ミリモル）を用いること、水およびオクタン酸を仕込まないこと、オートクレーブ内部の一酸化炭素／水素＝１／１（モル比）の混合ガス圧力を５．０ＭＰａ（ゲージ圧）一定として１８時間反応を行った以外は、実施例１と同様に反応を実施した。反応開始時の反応液中のロジウム濃度はロジウム原子として０．００７１ミリモル／ｋｇであり、ビスホスファイト使用量はロジウム原子に対して６．６７モル倍であった。
　反応後の７－オクテン－１－アールの転化率は９５．３％であり、ジアルデヒド選択率は９０．５％（直鎖／分岐比＝８４．６／１５．４）であり（ジアルデヒド収率：８６．２％）、異性体などの選択率は９．５％であった。 Reference Example 2 (Comparison with Example 3)
In Example 1, 17.7 mg (0.069 mmol) was used instead of 29.2 mg (0.113 mmol) of Rh (acac) (CO) 2, and 744.7 mg (0.009 mmol) of bisphosphite A was used. 759 mmol) is used instead of 451.0 mg (0.460 mmol), water and octanoic acid are not charged, and the mixture gas pressure of carbon monoxide / hydrogen = 1/1 (molar ratio) inside the autoclave is 5 The reaction was performed in the same manner as in Example 1 except that the reaction was performed for 18 hours at a constant 0.0 MPa (gauge pressure). The rhodium concentration in the reaction solution at the start of the reaction was 0.0071 mmol / kg as rhodium atoms, and the amount of bisphosphite used was 6.67 mol times the rhodium atoms.
The conversion of 7-octen-1-al after the reaction was 95.3%, and the dialdehyde selectivity was 90.5% (linear / branch ratio = 84.6 / 15.4) (dialdehyde). (Yield: 86.2%), and the selectivity for isomers and the like was 9.5%.
　実施例１では、反応開始時の反応液中の含水量は４３０ミリモル／ｋｇ、カルボン酸含有量はカルボキシル基として２０．８８ミリモル／ｋｇである。すなわち、ビスホスファイトＡに対して５６００モル倍以上の水および２６０モル倍以上のオクタン酸共存下で７－オクテン－１－アールをヒドロホルミル化反応している。特許文献１に示される、含水率７０ｐｐｍのトルエン１００ｍｌ中にビスホスファイト１００ｍｇを入れた際の１２５℃での残存率試験結果からは、ビスホスファイトの安定性が低く、触媒として機能し難いことが予想されるが、驚くべきことに、実施例１に示すとおり良好に反応が進行することがわかる。すなわち、反応開始時の反応液中の含水量が０．１～５００ミリモル／ｋｇ、かつ反応液中のカルボン酸の含有量がカルボキシル基として０．１～５０ミリモル／ｋｇである条件であっても、本発明の製造方法は良好に実施することができる。 In Example 1, the water content in the reaction solution at the start of the reaction is 430 mmol / kg, and the carboxylic acid content is 20.88 mmol / kg as a carboxyl group. That is, 7-octen-1-al is hydroformylated with bisphosphite A in the presence of 5600 mole times or more of water and 260 mole times or more of octanoic acid. From the result of the residual rate test at 125 ° C. when 100 mg of bisphosphite is added to 100 ml of toluene having a water content of 70 ppm shown in Patent Document 1, the stability of bisphosphite is low and it is difficult to function as a catalyst. It is surprisingly found that the reaction proceeds well as shown in Example 1. That is, the water content in the reaction solution at the start of the reaction is 0.1 to 500 mmol / kg, and the carboxylic acid content in the reaction solution is 0.1 to 50 mmol / kg as carboxyl groups. However, the production method of the present invention can be carried out satisfactorily.
　実施例２および参考例１より、１２時間の反応でジアルデヒドを収率８９．４％で得る際のロジウム使用量（反応開始時の反応液中のロジウム原子として濃度換算）は、実施例２では０．０１１６ミリモル／ｋｇであるのに対し参考例１では０．０１３４ミリモル／ｋｇである。すなわち、反応の進行に伴って反応圧力を低下させる本発明の製造方法を適用した実施例２は、反応圧力を一定圧力に維持した参考例１と比べロジウム使用量を約１３％削減できることがわかる。
　同様に、実施例３および参考例２より、１８時間の反応でジアルデヒドを収率８６．３％で得る際のロジウム使用量（反応開始時の反応液中のロジウム原子として濃度換算）は、実施例３では０．００６３ミリモル／ｋｇであるのに対し参考例２では０．００７１ミリモル／ｋｇである。すなわち、本発明の製造方法を適用した実施例３は、反応圧力を一定圧力に維持した参考例２と比べロジウム使用量を約１１％削減できることがわかる。
　かかる実施例より、反応の進行に伴って反応圧力を低下させる本発明の製造方法により、好適には、各々の分子末端にエチレン性二重結合およびアルデヒド基をそれぞれ有する直鎖状オレフィン性化合物の転化率が７０％を超えた段階において、圧力を段階的または連続的に反応開始時の圧力の３０～８０％となるように制御することにより、ロジウム使用量が削減でき、ジアルデヒドの製造単価削減に寄与することがわかる。
　実施例４および５より、本発明の製造方法はビスホスファイトＢおよびＣでも有効に実施できることがわかる。 From Example 2 and Reference Example 1, the amount of rhodium used (in terms of concentration as rhodium atoms in the reaction solution at the start of the reaction) when dialdehyde is obtained in a yield of 89.4% by reaction for 12 hours is as shown in Example 2. Is 0.0116 mmol / kg, whereas in Reference Example 1, it is 0.0134 mmol / kg. That is, it can be seen that Example 2 to which the production method of the present invention that reduces the reaction pressure as the reaction progresses can reduce the amount of rhodium used by about 13% compared to Reference Example 1 in which the reaction pressure is maintained at a constant pressure. .
Similarly, from Example 3 and Reference Example 2, the amount of rhodium used (in terms of the concentration of rhodium atoms in the reaction solution at the start of the reaction) when dialdehyde is obtained in a yield of 86.3% after 18 hours of reaction is In Example 3, it is 0.0063 mmol / kg, while in Reference Example 2, it is 0.0071 mmol / kg. That is, it can be seen that Example 3 to which the production method of the present invention is applied can reduce the amount of rhodium used by about 11% compared to Reference Example 2 in which the reaction pressure is maintained at a constant pressure.
From this example, the production method of the present invention in which the reaction pressure is reduced as the reaction proceeds, preferably, the linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular end, respectively. When the conversion rate exceeds 70%, the amount of rhodium used can be reduced by controlling the pressure to be 30 to 80% of the pressure at the start of the reaction stepwise or continuously. It turns out that it contributes to reduction.
From Examples 4 and 5, it can be seen that the production method of the present invention can also be effectively carried out with bisphosphites B and C.
　本発明の方法によれば、直鎖状ジアルデヒドと分岐状ジアルデヒドの生成比が８０／２０～９０／１０であるジアルデヒドを工業的に有利に製造できる。本発明の方法は、例えば、７－オクテン－１－アールから、１，９－ノナンジオールと２－メチル－１，８－オクタンジオールのジオール混合物（１，９－ノナンジオールの含有量８０～９０質量％）の合成中間体となる、１，９－ノナンジアール／２－メチル－１，８－オクタンジアール（ＮＬ／ＭＯＬ）のジアルデヒド混合物（ＮＬ／ＭＯＬ＝８０／２０～９０／１０）の製造方法として有用である。前記ジアルデヒド混合物からは１，９－ノナンジオールと２－メチル－１，８－オクタンジオールのジオール混合物が得られ、かかるジオール混合物は、ポリカーボネート、ポリエステル、ポリウレタンなどの製造原料、塗料（ポリエステル塗料、エポキシ樹脂塗料）原料、ポリエステル樹脂やエポキシ樹脂の樹脂改質剤などとして有用である。 According to the method of the present invention, a dialdehyde having a production ratio of linear dialdehyde to branched dialdehyde of 80/20 to 90/10 can be advantageously produced industrially. The method of the present invention is, for example, from 7-octen-1-al to a diol mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol (content of 1,9-nonanediol of 80 to 90). (Mass%) of 1,9-nonanediar / 2-methyl-1,8-octanediar (NL / MOL) dialdehyde mixture (NL / MOL = 80/20 to 90/10) It is useful as a production method. From the dialdehyde mixture, a diol mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol is obtained. Such a diol mixture is a raw material for production such as polycarbonate, polyester, polyurethane, paint (polyester paint, Epoxy resin paint) It is useful as a raw material, a resin modifier for polyester resins and epoxy resins.

Claims (8)

  1. 一般式（Ｉ）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒは水素原子、炭素数１～４のアルキル基または炭素数１～４のアルコキシ基を表し、Ｗは炭素数１～２０のアルキレン基、炭素数５～１８のシクロアルキレン基または炭素数７～１１のアルキレン－アリーレン基を表す。）
    で示されるビスホスファイトおよびロジウム化合物からなるロジウム触媒の存在下、各々の分子末端にエチレン性二重結合およびアルデヒド基をそれぞれ有する直鎖状オレフィン性化合物を、一酸化炭素および水素と反応させてジアルデヒドを製造する方法において、反応の進行に伴って、一酸化炭素および水素からなる混合ガスの反応圧力を低下させることを特徴とするジアルデヒドの製造方法。     Formula (I)
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, W represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 5 to 18 carbon atoms, or Represents an alkylene-arylene group having 7 to 11 carbon atoms.)
    In the presence of a rhodium catalyst comprising a bisphosphite and a rhodium compound represented by formula (1), a linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular end is reacted with carbon monoxide and hydrogen, respectively. A method for producing a dialdehyde, comprising reducing the reaction pressure of a mixed gas composed of carbon monoxide and hydrogen as the reaction proceeds.
  2. 反応開始時の反応液中の含水量が０．１～５００ミリモル／ｋｇでありかつ反応液中のカルボン酸の含有量がカルボキシル基として０．１～５０ミリモル／ｋｇであることを特徴とする、請求項１に記載のジアルデヒドの製造方法。 The water content in the reaction solution at the start of the reaction is 0.1 to 500 mmol / kg, and the carboxylic acid content in the reaction solution is 0.1 to 50 mmol / kg as carboxyl groups. The manufacturing method of the dialdehyde of Claim 1.
  3. 各々の分子末端にエチレン性二重結合およびアルデヒド基をそれぞれ有する直鎖状オレフィン性化合物の転化率が７０％を超えた段階において、一酸化炭素および水素からなる混合ガスの反応圧力を段階的または連続的に反応開始時の圧力の３０～８０％となるように制御することを特徴とする請求項１または２に記載のジアルデヒドの製造方法。 When the conversion rate of the linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular terminal exceeds 70%, the reaction pressure of the mixed gas composed of carbon monoxide and hydrogen is changed stepwise or The method for producing a dialdehyde according to claim 1 or 2, wherein the pressure is continuously controlled to be 30 to 80% of the pressure at the start of the reaction.
  4. 反応器を複数連結し、第１反応器において各々の分子末端にエチレン性二重結合およびアルデヒド基をそれぞれ有する直鎖状オレフィン性化合物の転化率が７０％を超えるまで反応を行い、次いで第１反応器中の反応液を、一酸化炭素および水素からなる混合ガスの反応圧力が第１反応器の３０～８０％である第２反応器に移送し、引続き反応を行う工程を有することを特徴とする、請求項３に記載のジアルデヒドの製造方法。 A plurality of reactors are connected, and the reaction is performed in the first reactor until the conversion rate of the linear olefinic compound having an ethylenic double bond and an aldehyde group at each molecular terminal exceeds 70%, and then the first reactor A step of transferring the reaction liquid in the reactor to a second reactor in which the reaction pressure of the mixed gas composed of carbon monoxide and hydrogen is 30 to 80% of that of the first reactor, and subsequently performing the reaction. The method for producing a dialdehyde according to claim 3.
  5. 各々の分子末端にエチレン性二重結合およびアルデヒド基をそれぞれ有する直鎖状オレフィン性化合物が５－ヘキセン－１－アール、６－ヘプテン－１－アール、７－オクテン－１－アール、８－ノネン－１－アール、９－デセン－１－アール、１０－ウンデセン－１－アール、１１－ドデセン－１－アールのいずれかである、請求項１～４のいずれかに記載のジアルデヒドの製造方法。 Linear olefinic compounds each having an ethylenic double bond and an aldehyde group at each molecular end are 5-hexen-1-al, 6-hepten-1-al, 7-octen-1-al, and 8-nonene. The method for producing a dialdehyde according to any one of claims 1 to 4, which is any one of 1-al, 9-decene-1-al, 10-undecene-1-al, and 11-dodecene-1-al .
  6. 一般式（Ｉ）において、Ｒが炭素数１～４のアルキル基または炭素数１～４のアルコキシ基であり、Ｗが炭素数１～２０のアルキレン基であるビスホスファイトを用いることを特徴とする、請求項１～５のいずれかに記載のジアルデヒドの製造方法。 In the general formula (I), R is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and bisphosphite in which W is an alkylene group having 1 to 20 carbon atoms is used. The method for producing a dialdehyde according to any one of claims 1 to 5.
  7. Ｒがｔ－ブチル基であり、Ｗが炭素数２～５のアルキレン基であるビスホスファイトを用いることを特徴とする、請求項６に記載のジアルデヒドの製造方法。 The method for producing a dialdehyde according to claim 6, wherein bisphosphite wherein R is a t-butyl group and W is an alkylene group having 2 to 5 carbon atoms is used.
  8. 反応液中のロジウム使用量がロジウム原子として１．０×１０－４～６．０×１０－１ミリモル／ｋｇであり、ビスホスファイトの使用量がロジウム原子に対して１～１００モル倍であり、反応温度が５０～１３０℃であり、一酸化炭素および水素の組成比がモル比として一酸化炭素／水素＝０．１／１～１０／１でかつ反応開始時の圧力が０．５～１０ＭＰａ（ゲージ圧）である、 請求項１～７のいずれかに記載のジアルデヒド化合物の製造方法。 The amount of rhodium used in the reaction solution is 1.0 × 10 −4 to 6.0 × 10 −1 mmol / kg as rhodium atoms, and the amount of bisphosphite used is 1 to 100 mol times the amount of rhodium atoms. The reaction temperature is 50 to 130 ° C., the composition ratio of carbon monoxide and hydrogen is carbon monoxide / hydrogen = 0.1 / 1 to 10/1 as a molar ratio, and the pressure at the start of the reaction is 0.5 The method for producing a dialdehyde compound according to any one of claims 1 to 7, wherein the method is -10 MPa (gauge pressure).
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017175582A1 (en) * 2016-04-05 2017-10-12 株式会社クラレ Bisphosphite and method of producing 1,9-nonanedial using same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3424897A4 (en) * 2016-03-01 2019-10-09 Kuraray Co., Ltd. Method of producing dialdehyde compound

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62270541A (en) * 1986-05-20 1987-11-24 Mitsui Toatsu Chem Inc Production of 2-chloropropionaldehyde
JPH11511159A (en) * 1995-08-21 1999-09-28 ビーエーエスエフ アクチェンゲゼルシャフト Method for purifying liquid hydroformylation effluent
JP2004506602A (en) * 2000-02-14 2004-03-04 ビーエーエスエフ　アクチェンゲゼルシャフト Method for post-treating liquid hydroformylation effluent
JP2007509093A (en) * 2003-10-21 2007-04-12 ビーエーエスエフ　アクチェンゲゼルシャフト Continuous production method of aldehyde
WO2007114445A1 (en) * 2006-04-04 2007-10-11 Kuraray Co., Ltd. Method for producing aldehyde using bisphosphite and group 8-10 metal compound, and such bisphosphite
JP2008031125A (en) 2006-07-31 2008-02-14 Kuraray Co Ltd Method for producing aldehyde
JP2012522813A (en) * 2009-04-07 2012-09-27 オクセア・ゲゼルシャフト・ミト・べシュレンクテル・ハフツング Finishing process for liquid hydroformylation products.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4808756A (en) 1986-04-07 1989-02-28 Kuraray Co., Ltd. Method for production of α,ω-dialdehydes
CN1222904A (en) 1996-04-24 1999-07-14 联合碳化化学品及塑料技术公司 Processes for producing hydroxyaldehydes
CN100412046C (en) 2003-10-21 2008-08-20 巴斯福股份公司 Method for the continuous production of aldehydes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62270541A (en) * 1986-05-20 1987-11-24 Mitsui Toatsu Chem Inc Production of 2-chloropropionaldehyde
JPH11511159A (en) * 1995-08-21 1999-09-28 ビーエーエスエフ アクチェンゲゼルシャフト Method for purifying liquid hydroformylation effluent
JP2004506602A (en) * 2000-02-14 2004-03-04 ビーエーエスエフ　アクチェンゲゼルシャフト Method for post-treating liquid hydroformylation effluent
JP2007509093A (en) * 2003-10-21 2007-04-12 ビーエーエスエフ　アクチェンゲゼルシャフト Continuous production method of aldehyde
WO2007114445A1 (en) * 2006-04-04 2007-10-11 Kuraray Co., Ltd. Method for producing aldehyde using bisphosphite and group 8-10 metal compound, and such bisphosphite
JP2008031125A (en) 2006-07-31 2008-02-14 Kuraray Co Ltd Method for producing aldehyde
JP2012522813A (en) * 2009-04-07 2012-09-27 オクセア・ゲゼルシャフト・ミト・べシュレンクテル・ハフツング Finishing process for liquid hydroformylation products.

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF AMERICAN CHEMICAL SOCIETY, vol. 114, 1992, pages 5535 - 5543
ORGANOMETALLICS, vol. 14, 1995, pages 3832 - 3838
See also references of EP2980060A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017175582A1 (en) * 2016-04-05 2017-10-12 株式会社クラレ Bisphosphite and method of producing 1,9-nonanedial using same

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